Functionalized Organogold(I) Complexes From

FUNCTIONALIZED ORGANOGOLD(I) COMPLEXES FROM

BASE-PROMOTED AURATION,

COPPER(I)-CATALYZED HUISGEN 1,3-DIPOLAR CYCLOADDITION

AND HORNER-WADSWORTH-EMMONS REACTIONS

AND

METALLO-AZADIPYRROMETHENE COMPLEXES

FOR SOLAR ENERGY CONVERSION AND OXYGEN EVOLUTION

LEI GAO

Submitted in Partial Fulfillment of the Requirements

For the Degree of Doctor of Philosophy

Department of Chemistry

CASE WESTERN RESERVE UNIVERSITY

August, 2010

CASE WESTERN RESERVE UNIVERSITY

SCHOOL OF GRADUATE STUDIES

We hereby approve the thesis/dissertation of

______

candidate for the ______degree *.

(signed)______(chair of the committee)

______

(date) ______

*We also certify that written approval has been obtained for any proprietary material contained therein.

TToo tthhee oonneess II lloovvee tthhee MMoosstt 献给我最爱的亲人

My Parents, My Sister, My Brother, My Little Nephew and My Jamie

我敬爱的父母, 我亲爱的姐姐弟弟, 我可爱的小外甥, 以及我生命的另一半 Jamie.

With Them, My Life is Full of Happiness

有了他们, 我的人生充满了喜悦.

Table of Contents

Table of contents i

List of Figures iv

List of Schemes xv

List of Tables xviii

List of Boxes xxvi

Acknowledgements xxvii

List of Abbreviations xxviii

Abstract xxxiii

Chapter 1. General Introduction

1.1. The Chemistry of Gold 1

1.2. Copper(I)-Catalyzed Click Chemistry of Huisgen 11

Azide-Alkyne 1,3-Dipolar Cycloaddition

1.3. Two-Photon Absorbing Chromophores 16

1.4. Azadipyrromethenes 22

1.5. Proposed Research 29

1.6. References 37

Chapter 2. Synthesis and Characterization of Mono- and Di-Gold(I) Naphthalene

Complexes from Base-Promoted Auration

2.1. Introduction 54

2.2. Results and Discussions 60

2.3. Conclusions 74

2.4. Experimental 76

2.5. References 88

Chapter 3. Copper-Catalyzed Huisgen [3+2] Cycloaddition of Gold(I) Alkynyls with

Benzyl Azide

3.1. Introduction 91

3.2. Results and Discussions 96

3.3. Conclusions 108

3.4. Experimental 110

3.5. References 127

Chapter 4. Two-Photon Absorbing Gold(I) Styryl Benzene and Naphthalene

Complexes

4.1. Introduction 131

4.2. Results and Discussions 136

4.3. Conclusions 150

4.4. Experimental 152

4.5. References 169

Chapter 5. Metalloazadipyrromethene Complexes for Solar Energy Conversion and

Oxygen Evolution

5.1. Introduction 171

5.2. Results and Discussions 180

5.3. Conclusions 197

5.4. Experimental 199

5.5. References 208

Chapter 6. Thesis Summary and Future Directions

6.1. Thesis Summary 212

6.2. Future Directions 217

6.3 References 219

Appendix I. X-Ray Crystallographic Data for Collected Crystal Structures 220

Appendix II. NMR Spectra of Slected Compounds 342

Appendix III. Absorption and Emission Spectra of Selected Compounds 432

Bibliography 448

iii

List of Figures

Figure Page

1.1.1. Distribution of the Crystal Structures of CuI, AgI, and AuI Compounds 2

According to Coordination Number of the Metal Atom as Found

in the Cambridge Structural Database

1.1.2. Calculated Relativistic Contraction of the 6s Orbital 4

1.3.1. Equations for the 2PA Cross Section Calculation 17

1.3.2. Energy Level Diagrams for the Essential States 18

1.4.1. Core Structures of Azadipyrromethenes 22

1.4.2. Core Structures of BODIPY, dipyrromethenes and dipyrromethanes 23

with their numbering systems

1.4.3. Functional Azadipyrromethenes 26

1.4.4. Reported Metallo-Azadipyrromethene Complexes 28

1.5.1. Synthetic Targets of Two-Photon Absorbing Gold(I) Complexes 32

1.5.2. Storing Solar Energy in Chemical Bonds 33

2.1.1. Naphthalene with its Numbering System 56

2.1.2. Absorption and emission of naphthalene in CH2Cl2 57

2.1.3. Emission Quenching of PCy3Au-1-Naphthyl by Methyl Viologen 57

2.2.1. Absorption and emission spectra for all the ligands 63

2.2.2. Crystal structures (100 K) of phosphine gold(I)-naphthyl complexes 68

2.2.3. Absorption and Emission Spectra of Mono- and 71

Di-gold(I) Naphthyl Complexes

3.2.1. Crystal structures (100 K) of compound (SIPr)Au(2-naphthylethynyl) 98

3.2.2. Absorption and emission spectra for (SIPr)Au(2-naphthylethynyl) 99

3.2.3. Crystal Structure (100 K) of 105

[(SIPr)Au(1-benzyl-4-(2-naphthyl)triazolato)]

3.2.4. Room-temperature absorption and Emission 106

spectra of [(SIPr)Au(1-benzyl-4-(2-naphthyl)triazolato)] in THF

4.1.1. Jablonski Diagram of Singlet Oxygen Generation in One 134

and Two-Photon Excitations

4.2.1. Crystal Structures of Two-Photon Absorbing Gold(I) Compounds 143

4.2.2. The Dihedral angle between best fit-planes along the long and 144

short axis of the tetragold alkynyl compound

4.2.3. Normalized absorption of spectra of gold(I) complexes 146

with direct and indirect Au–Caromatic bonds

4.2.4. Two-Photon absorbing gold(I) Compounds arranged by the intensity 148

of their colors in dichloromethane and their emission under UV irradiation

5.1.1. Azadipyrromethene Ligands 174

5.1.2. Solar Energy Conversion by M-Azadipyrromethene Complexes 174

5.1.3. The Azadipyrromethene Molecule Supporting Four-Coordiantion 178

Geometry

5.2.1. Crystal Structures (100 K) of Gold(I) Azadipyrromethene Complexes 183

5.2.2. Absorption and Emission Spectra Azadipyrromethene Ligand 186

and the Corresponding Gold(I) Complex

5.2.3. Steady state emission spectra collected at 77 K in 2-MeTHF 187

5.2.4. Crystal structures of Collected Metallo-azadipyrromethene Complexes 193

5.2.5. Absorption and Emission Spectra for LOH and ZnLOH in Acetone 194

5.2.6. Absorption spectra of VOLOH in THF 195

5.2.7. Absorption spectra of MnLOH in THF 196

AI-1a. ORTEP plot of PCy3Au-2-naphthyl 221

AI-2a. ORTEP plot of 2,6-Bis(PCy3Au)-naphthalene 224

AI-3a. ORTEP plot of 2,7-Bis(PCy3Au)-naphthalene 228

AI-4a. ORTEP plot of PPh3Au-2-naphthyl 234

AI-5a. ORTEP plot of 2,6-Bis(PPh3Au)-naphthalene 237

AI-6a. ORTEP plot of 2,7-Bis(PPh3Au)-naphthalene 240

AI-7a. ORTEP plot of [(SIPr)Au(2-naphthylethynyl)] 244

AI-8a. ORTEP plot of [(SIPr)Au(ferrocenylethynyl)] 248

AI-9a. ORTEP plot of [(SIPr)Au(1-pyrenylethynyl)] 253

AI-10a. ORTEP plot of [(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)] 257

AI-11a. ORTEP plot of [(SIPr)Au(1-benzyl-4-tert-butyltriazolato)] 261

AI-12a. ORTEP plot of [(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)] 266

AI-13a. ORTEP plot of [(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)] 272

AI-14a. ORTEP plot of [(PPh3)Au(1-benzyl-4-phenyltriazolato)] 275

AI-15a. ORTEP plot of [(PPh3)Au(1-benzyl-(4-tolyl)triazolato)] 278

AI-16a. ORTEP plot of [(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)] 282

AI-17a. ORTEP plot of [(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)] 285

AI-18a. ORTEP plot of (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene 293

AI-19a. ORTEP plot of 1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene 297

AI-20a. ORTEP plot of 301

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AI-21a. ORTEP plot of (PPhMe2Au)LaBr2 305

AI-22a. ORTEP plot of (PPhMe2Au)LaBr2 309

AI-23a. ORTEP plot of (PPhMe2Au)LbBr2 313

AI-24a. ORTEP plot of (PPhMe2Au)LcBr2 319

AI-25a. ORTEP plot of Zn azadipyrromethene complex 323

AI-26a. ORTEP plot of VO azadipyrromethene complex 330

AI-27a. ORTEP plot of Mn azadipyrromethene complex 334

AI-28a. ORTEP plot of Fe azadipyrromethene complex 339

AII-1. 1H NMR Spectrum of 2,6-di(Bpin)Naphthalene 342

AII-2. 1H NMR Spectrum of 2,7-di(Bpin)Naphthalene 343

31 1 AII-3. P{ H} NMR Spectrum of PCy3Au-2-Naphthyl 344

1 AII-4. H NMR Spectrum of PCy3Au-2-Naphthyl 345

31 1 AII-5. P{ H} NMR Spectrum of 2,6-bis(PCy3Au)naphthalene 346

1 AII-6. H NMR Spectrum of 2,6-bis(PCy3Au)naphthalene 347

31 1 AII-7. P{ H} NMR Spectrum of 2,7-bis(PCy3Au)naphthalene 348

1 AII-8. H NMR Spectrum of 2,7-bis(PCy3Au)naphthalene 349

31 1 AII-9. P{ H} NMR Spectrum of PPh3Au-2-naphthyl 350

1 AII-10. H NMR Spectrum of PPh3Au-2-naphthyl 351

31 1 AII-11. P{ H} NMR Spectrum of 2,6-bis(PPh3Au)naphthalene 352 vii

31 AII-12. H NMR Spectrum of 2,6-bis(PPh3Au)naphthalene 353

31 1 AII-13. P{ H} NMR Spectrum of 2,7-bis(PPh3Au)naphthalene 354

1 AII-14. H NMR Spectrum of 2,7-bis(PPh3Au)naphthalene 355

AII-15. 1H NMR Spectrum of SIPrAu-2-naphthyl 356

AII-16. 13C{1H} NMR Spectrum of SIPrAu-2-naphthyl 357

AII-17. 1H NMR Spectrum of 2,6-bis(SIPrAu)naphthalene 358

AII-18. 13C{1H} NMR Spectrum of 2,6-bis(SIPrAu)naphthalene 359

AII-19. 1H NMR Spectrum of 2,7-bis(SIPrAu)naphthalene 360

AII-20. 13C{1H} NMR Spectrum of 2,7-bis(SIPrAu)naphthalene 361

AII-21. 1H NMR Spectrum of SIPrAu-tert-bytylethynyl 362

AII-22. 1H NMR Spectrum of SIPrAu-2-naphthylethynyl 363

AII-23. 13C{1H} NMR Spectrum of SIPrAu-1-naphthylethynyl 364

AII-24. 1H NMR Spectrum of SIPrAu-2-pyrenylethynyl 365

AII-25. 13C{1H} NMR Spectrum of SIPrAu-1-pyrenylethynyl 366

AII-26. 1H NMR Spectrum of SIPrAu-ferrocenylethynyl 367

AII-27. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-(2-naphthyl)triazolato) 368

AII-28. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-tert-butyltriazolato) 369

AII-29. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-ferrocenyltriazolato) 370

AII-30. 31P{1H} NMR Spectrum of 371

PPh3Au-(1-benzyl-4-carboxylmethyltriazolato)

1 AII-31. H NMR Spectrum of PPh3Au-(1-benzyl-4-carboxylmethyltriazolato) 372

31 1 AII-32. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-phenyltriazolato) 373

viii

1 AII-33. H NMR Spectrum of PPh3Au-(1-benzyl-4-phenyltriazolato) 374

1 AII-34. H NMR Spectrum of PPh3Au-(1-benzyl-4-(4-tolyl)triazolato) 375

1 AII-35. H NMR Spectrum of PPh3Au-(1-benzyl-4-(4-tolyl)triazolato) 376

AII-36. 31P{1H} NMR Spectrum of 377

PPh3Au-(1-benzyl-4-(4-fluorophenyl)triazolato)

1 AII-37. H NMR Spectrum of PPh3Au-(1-benzyl-4-(4-fluorophenyl)triazolato) 378

31 1 AII-38. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-(3-thienyl)triazolato) 379

1 AII-39. H NMR Spectrum of PPh3Au-(1-benzyl-4-(3-thienyl)triazolato) 380

31 1 AII-40. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-ferrocenyltriazolato) 381

1 AII-41. H NMR Spectrum of PPh3Au-(1-benzyl-4-ferrocenyltriazolato) 382

31 1 AII-42. P{ H} NMR Spectrum of PCy3Au-(1-benzyl-4-(4-biphenyl)triazolato) 383

1 AII-43. H NMR Spectrum of PCy3Au-(1-benzyl-4-(4-biphenyl)triazolato) 384

31 1 AII-44. P{ H} NMR Spectrum of PCy3Au-(1-benzyl-4-(1-naphthyl)triazolato) 385

1 AII-45. H NMR Spectrum of PCy3Au-(1-benzyl-4-(1-naphthyl)triazolato) 386

31 1 AII-46. P{ H} NMR Spectrum of PCy3Au-(1-benzyl-4-(2-naphthyl)triazolato) 387

1 AII-47. H NMR Spectrum of PCy3Au-(1-benzyl-4-(2-naphthyl)triazolato) 388

AII-48. 31P{1H} NMR Spectrum of 389

PCy3Au-(1-benzyl-4-(9-phenanthryl)triazolato)

1 AII-49. H NMR Spectrum of PCy3Au-(1-benzyl-4-(9-phenanthryl)triazolato) 390

AII-50. 1H NMR spectrum of 1,4-dibromo-2,5-bis(4-tert-butylstyryl)benzene 391

AII-51. 1H NMR spectrum of 1,4-dibromo-2,5-bis(4-bromostyryl)benzene 392

AII-52. 1H NMR spectrum of 1-Bpin-4-(4-tert-butylstyryl)benzene 393

AII-53. 1H NMR spectrum of 1,4-bis(Bpin)-2,5-bis(4-tert-butylstyryl)benzene 394

AII-54. 1H NMR spectrum of 1,4-bis(4-Bpin-styryl)benzene 395

AII-55. 1H NMR spectrum of 1,4-bis(Bpin)-2,5-bis(4-Bpin-styryl)benzene 396

AII-56. 31P{1H} NMR spectrum of 397

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

1 AII-57. H NMR spectrum of (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene 398

AII-58. 31P{1H} NMR spectrum of 399

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AII-59. 1H NMR spectrum of 400

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AII-60. 31P{1H} NMR spectrum of 401

2,5-bis(4-tert-butylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AII-61. 1H NMR spectrum of 402

2,5-bis(4-tert-butylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AII-62. 31P{1H} NMR spectrum of 403

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AII-63. 1H NMR spectrum of 404

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

31 1 AII-64. P{ H} NMR spectrum of 1,4-bis(4-[(PCy3)Au]styryl)benzene 405

1 AII-65. H NMR spectrum of 1,4-bis(4-[(PCy3)Au]styryl)benzene 406

AII-66. 31P{1H} NMR spectrum of 407

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

AII-67. 1H NMR spectrum of 408

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

AII-68. 31P{1H} NMR spectrum of 409

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

AII-69. 1H NMR spectrum of 410

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

AII-70. 31P{1H} NMR spectrum of 411

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

AII-71. 1H NMR spectrum of 412

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

31 1 AII-72. P{ H} NMR spectrum of 2,6-bis(4-[(PCy3)Au]styryl)naphthalene 413

1 AII-73. H NMR spectrum of 2,6-bis(4-[(PCy3)Au]styryl)naphthalene 414

AII-74. 31P{1H} NMR spectrum of 415

2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene

1 AII-75. H NMR spectrum of 2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene 416

AII-76. 31P{1H} NMR spectrum of 417

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

AII-77. 1H NMR spectrum of 418

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

AII-78. 31P{1H} NMR spectrum of 419

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

AII-79. 1H NMR spectrum of 420

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

AII-80. 1H NMR spectrum of 421

(0Z)-N-(3,5-bis(4-bromophenyl)-2H-pyrrol-2-ylidene)-3,5-bis(4-bromophen

yl)-1H-pyrrol-2-amine (Ld)

31 1 AII-81. P{ H} NMR spectrum of PMe2PhAuLd 422

1 AII-82. H NMR spectrum of PMe2PhAuLd 423

31 1 AII-83. P{ H} NMR spectrum of PMe2PhAuLaBr2 424

1 AII-84. H NMR spectrum of PMe2PhAuLaBr2 425

31 1 AII-85. P{ H} NMR spectrum of PMe2PhAuLbBr2 426

1 AII-86. H NMR spectrum of PMe2PhAuLbBr2 427

31 1 AII-87. P{ H} NMR spectrum of PMe2PhAuLcBr2 428

1 AII-88. H NMR spectrum of PMe2PhAuLcBr2 429

31 1 AII-89. P{ H} NMR spectrum of PMe2PhAuLdBr2 430

1 AII-90. H NMR spectrum of PMe2PhAuLdBr2 431

AIII-1. Absorption and Emission Spectra of 2,6-dibromonaphthalene 432

AIII-2. Absorption and Emission Spectra of 2,7-dibromonaphthalene 432

AIII-3. Absorption and Emission Spectra of PPh3Au-2-naphthyl 433

AIII-4. Absorption and Emission Spectra of 2,6-(PPh3Au)-naphthyl 433

AIII-5. Absorption and Emission Spectra of 2,7-(PPh3Au)-naphthyl 434

AIII-6. Absorption and Emission Spectra of SIPrAu-2-naphthyl 434

AIII-7. Absorption and Emission Spectra of 2,6-(SIPrAu)-naphthyl 435

AIII-8. Absorption and Emission Spectra of 2,7-(SIPrAu)-naphthyl 435

xii

AIII-9. Absorption and Emission Spectra of PCy3Au(9-phenanthrylethynyl) 436

AIII-10. Absorption and Emission Spectra of SIPrAu(1-pyrenylethynyl) 436

AIII-11. Absorption and Emission Spectra of 437

PCy3Au(1-benzyl-4-(4-biphenyl)triazolato)

AIII-12. Absorption and Emission Spectra of 437

PCy3Au(1-benzyl-4-(1-naphthyl)triazolato)

AIII-13. Absorption and Emission Spectra of 438

PCy3Au(1-benzyl-4-(2-naphthyl)triazolato)

AIII-14. Absorption and Emission Spectra of 438

PCy3Au(1-benzyl-4-(9-phenanthryl)triazolato)

AIII-15. Absorption and Emission Spectra of 439

1-bpin-4-(4-tert-butylstyryl)benzene

AIII-16. Absorption and Emission Spectra of 1,4-bis(4-bpin-styryl)benzene 439

AIII-17. Absorption and Emission Spectra of 440

1,4-bis(bprin)-2,5-bis(4-bpin-styryl)benzne

AIII-18. Absorption and Emission Spectra of 440

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

AIII-19. Absorption and Emission Spectra of 441

2,5-bis(4-tert-butylstyryl)-1,4-bis([(PCy3)Au]ethynyl)benzene

AIII-20. Absorption and Emission Spectra of 441

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AIII-21. Absorption and Emission Spectra of 442

xiii

1,4-bis(4-[(PCy3)Au]styryl)benzene

AIII-22. Absorption and Emission Spectra of 442

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

AIII-23. Absorption and Emission Spectra of 443

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

AIII-24. Absorption and Emission Spectra of 443

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

AIII-25. Absorption and Emission Spectra of 444

2,6-bis(4-[(PCy3)Au]styryl)naphthalene

AIII-26. Absorption and Emission Spectra of 444

2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene

AIII-27. Absorption and Emission Spectra of 445

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

AIII-28. Absorption and Emission Spectra of 445

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

AIII-29. Absorption and Emission Spectra of PMe2PhAuLaBr2 446

AIII-30. Absorption and Emission Spectra of PMe2PhAuLbBr2 446

AIII-31. Absorption and Emission Spectra of PMe2PhAuLcBr2 447

xiv

List of Schemes

Scheme Page

1.1.1. Coordination Patterns of Different Gold Centers 3

1.1.2. Aurophilic Interaction in L–Au–L Dimers 6

1.1.3. Examples of Au(I) Phosphine Antitumor Complexes 9

1.2.1. Cu(I) Catalyzed 1,3-Dipolar Huisgen Cycloaddition 12

1.2.2. Proposed Catalytic Cycle for CuAAC 15

1.4.1. Synthetic Pathways for Azadipyrromethenes 24

1.4.2. Functionalizing Aza-BODIPY with Copper(I) Catalyzed 26

1,3-Dipolar Alkyne-Azide Cycloaddition

1.5.1. Au–C formation from Base-Promoted Auration 29

1.5.2. Cu(I)-Catalyzed 1,3-Dipolar Cycloaddition of Gold(I) 31

Alkynyl and Benzyl Azide

1.5.3. Synthetic Strategy for Gold(I) Azadipyrromethene Complexes 34

1.5.4. Synthetic Strategy for Zinc, Vanadyl, 35

Manganese and Iron Complexes

2.1.1. Base Promoted Auration of Napathalene at the 1-Position 56

2.2.1. Synthetic pathway for borylated naphthalenes 61

2.2.2. Synthetic diagram for the gold(I) naphthyl complexes 64

2.2.3. Triplet-state emission quantum yield calculation details 73

3.1.1. Uncatalyzed Cycloaddition Reactions of Gold(I) 93

3.1.2. Cycloaddition Isomers 93

3.1.3. Examples of Cu(I) Catalyzed Cycloaddition of Benzyl Azide 94

and an Internal Alkyne

3.2.1. Reaction sequence of Cu(I)-Catalyzed Cycloaddition of 96

Unstrained Gold(I) Internal Alkynyls and Benzyl Azide

3.2.2. New gold(I) alkynyl complexes 97

3.2.3. Cu(I)-Catalyzed Cycloaddition of 103

Gold(I) Alkynyls with 1-Azidoadamantane

4.1.1. Examples of Linear Centrosymmetric Oligo(arylenevinylenes) 132

4.1.2. Common Reaction Sequence to Build Distryryl Benzene Systems 132

4.1.3. Strong π-Electron Acceptor, BMes2 133

4.2.1. Synthesized Two-Photon Absorbing Gold(I) Complexes 136

4.2.2. Synthetic Pathway for (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene 137

4.2.3. Synthetic Pathway for Distyryl Benzene Gold(I) 138

Two-Photon Absorbing Complexes

4.2.4. Synthetic Pathway for Gold(I) Two-Photon Absorbing Complexes 139

with Alkynyl Bridges

4.2.5. Synthetic Pathway for Distyryl Naphthalene Gold(I) 140

Two-Photon Absorbing Complexes

5.1.1. Photogeneration of H2 from Rh(I) dimers 172

5.1.2. Four-Electron Photochemistry of Dirhodium Cores 172

5.1.3. Photocatalytic Generation of H2 from Rh2dfpma in Nonaqueous solutions 172

5.1.4. O2 evolution from a Mn2-prophyrin dimer and chlorite dismustase 178

xvi

5.2.1. Synthetic Scheme for Azadipyrromethenes, Brominated 181

Azadipyrromethanes, and Gold(I) Azadipyrromethene Complexes

5.2.2. Synthetic Pathways for Au(III) Azadipyrromethene Complexes 189

5.2.3. Reaction of LBr2Au(I) with Br2 190

5.2.4. Synthesis of Zinc, Vanadyl, Manganese, and Iron 192

Azadipyrromethene Complexes

6.1.1. Synthesis of Organogold(I) Complexes 212

6.1.2. Metalloazadipyrromethene Complexes for 215

Solar Energy Conversion and Oxygen Evolution

xvii

List of Tables

Table Page

2.2.1 Gold(I) naphthyl complexes from base-promoted Auration 66

31 1 2.2.2. P{ H} chemical shifts relative to 85% H3PO4(aq) of 67

phosphine-ligated gold complexes

2.2.3. 13C{1H} chemical shifts of ligand carbene carbons relative to 67

tetramethylsilane in NHC-ligated gold complexes

2.2.4. Selected interatomic distances (Å) and angles (°) for aurated naphthalenes 69

2.2.5. Luminescence parameters of gold-substituted naphthalenes 72

3.2.1 Selected Interatomic Distances (Å) in Crystallographically 99

Characterized Gold(I) Complexes

3.2.2. Selected Interatomic Angles (°) 99

3.2.3. Luminescence maxima (273 ± 2 K) of emissive compounds 100

in THF solution

3.2.4. Synthesis of Gold(I) Triazolate Complexes 102

3.2.5. Selected Interatomic Distances (Å) and Interatomic 105

Angles (°)a in Crystallographically Characterized Gold(I) Complexes

3.2.6. Emission lifetimes τ and quantum yields φem of luminescent 107

compounds in 2-MeTHF solution (room temperature) or glass (77 K)

4.2.1. 31P{1H} chemical shifts of the gold(I) styryl benzene complexes 142

4.2.2. Selected Interatomic Distances (Å) and Interatomic 145

Angles (°)a in Crystallographically Characterized Gold(I) Complexes

xviii

4.2.3. Emission Maxima and Quantum Yields 149

of the Gold(I) Styryl Benzene Complexes

5.2.1. 31P{1H} Chemical Shifts of the Gold(I) Azadipyrromethene Complexes 183

5.2.2. Selected Interatomic Distances (Å) and Interatomic Angles (°)a 184

in Crystallographically Characterized Gold(I) Azadipyrromethene Complexes

5.2.3. Absorption and Emission Maxima of the Gold(I) 187

Azadipyrromethene Complexes

AI-1a. Crystallographic data for PCy3Au-2-naphthyl 220

AI-1b. Data collection for PCy3Au-2-naphthyl 220

AI-1c. Refinement parameters of PCy3Au-2-naphthyl 221

AI-1d. Selected geometric parameters (Å, º) for PCy3Au-2-naphthyl 221

AI-2a. Crystallographic data for 2,6-Bis(PCy3Au)-naphthalene 223

AI-2b. Data collection for 2,6-Bis(PCy3Au)-naphthalene 223

AI-2c. Refinement parameters of 2,6-Bis(PCy3Au)-naphthalene 224

AI-2d. Selected geometric parameters (Å, º) for 2,6-Bis(PCy3Au)-naphthalene 224

AI-3a. Crystallographic data for 2,7-Bis(PCy3Au)-naphthalene 227

AI-3b. Data collection for 2,7-Bis(PCy3Au)-naphthalene 227

AI-3c. Refinement parameters of 2,7-Bis(PCy3Au)-naphthalene 228

AI-3d. Selected geometric parameters (Å, º) for 2,7-Bis(PCy3Au)-naphthalene 228

AI-4a. Crystallographic data for PPh3Au-2-naphthyl 233

AI-4b. Data collection for PPh3Au-2-naphthyl 233

AI-4c. Refinement parameters of PPh3Au-2-naphthyl 234

xix

AI-4d. Selected geometric parameters (Å, º) for PPh3Au-2-naphthyl 234

AI-5a. Crystallographic data for 2,6-Bis(PPh3Au)-naphthalene 236

AI-5b. Data collection for 2,6-Bis(PPh3Au)-naphthalene 236

AI-5c. Refinement parameters of 2,6-Bis(PPh3Au)-naphthalene 237

AI-5d. Selected geometric parameters (Å, º) for 2,6-Bis(PPh3Au)-naphthalene 237

AI-6a. Crystallographic data for 2,7-Bis(PPh3Au)-naphthalene 239

AI-6b. Data collection for 2,7-Bis(PPh3Au)-naphthalene 239

AI-6c. Refinement parameters of 2,7-Bis(PPh3Au)-naphthalene 240

AI-6d. Selected geometric parameters (Å, º) for 2,7-Bis(PPh3Au)-naphthalene 240

AI-7a. Crystallographic data for [(SIPr)Au(2-naphthylethynyl)] 243

AI-7b. Data collection for [(SIPr)Au(2-naphthylethynyl)] 243

AI-7c. Refinement parameters of [(SIPr)Au(2-naphthylethynyl)] 244

AI-7d. Selected geometric parameters (Å, º) for [(SIPr)Au(2-naphthylethynyl)] 244

AI-8a. Crystallographic data for [(SIPr)Au(ferrocenylethynyl)] 247

AI-8b. Data collection for [(SIPr)Au(ferrocenylethynyl)] 247

AI-8c. Refinement parameters of [(SIPr)Au(ferrocenylethynyl)] 248

AI-8d. Selected geometric parameters (Å, º) for [(SIPr)Au(ferrocenylethynyl)] 248

AI-9a. Crystallographic data for [(SIPr)Au(1-pyrenylethynyl)] 252

AI-9b. Data collection for [(SIPr)Au(1-pyrenylethynyl)] 252

AI-9c. Refinement parameters of [(SIPr)Au(1-pyrenylethynyl)] 253

AI-9d. Selected geometric parameters (Å, º) for [(SIPr)Au(1-pyrenylethynyl)] 253

AI-10a. Crystallographic data for [(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)] 256

AI-10b. Data collection for [(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)] 256

AI-10c. Refinement parameters of 257

[(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)]

AI-10d. Selected geometric parameters (Å, º) for 257

[(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)]

AI-11a. Crystallographic data for [(SIPr)Au(1-benzyl-4-tert-butyltriazolato)] 260

AI-11b. Data collection for [(SIPr)Au(1-benzyl-4-tert-butyltriazolato)] 260

AI-11c. Refinement parameters of [(SIPr)Au(1-benzyl-4-tert-butyltriazolato)] 261

AI-11d. Selected geometric parameters (Å, º) for 261

[(SIPr)Au(1-benzyl-4-tert-butyltriazolato)]

AI-12a. Crystallographic data for [(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)] 265

AI-12b. Data collection for [(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)] 265

AI-12c. Refinement parameters of [(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)] 266

AI-12d. Selected geometric parameters (Å, º) for 266

[(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)]

AI-13a. Crystallographic data for 271

[(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)]

AI-13b. Data collection for 271

[(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)]

AI-13c. Refinement parameters of 272

[(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)]

AI-13d. Selected geometric parameters (Å, º) for 272

xxi

[(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)]

AI-14a. Crystallographic data for [(PPh3)Au(1-benzyl-4-phenyltriazolato)] 274

AI-14b. Data collection for [(PPh3)Au(1-benzyl-4-phenyltriazolato)] 274

AI-14c. Refinement parameters of [(PPh3)Au(1-benzyl-4-phenyltriazolato)] 275

AI-14d. Selected geometric parameters (Å, º) for 275

[(PPh3)Au(1-benzyl-4-phenyltriazolato)]

AI-15a. Crystallographic data for [(PPh3)Au(1-benzyl-(4-tolyl)triazolato)] 277

AI-15b. Data collection for [(PPh3)Au(1-benzyl-(4-tolyl)triazolato)] 277

AI-15c. Refinement parameters of [(PPh3)Au(1-benzyl-(4-tolyl)triazolato)] 278

AI-15d. Selected geometric parameters (Å, º) for 278

[(PPh3)Au(1-benzyl-(4-tolyl)triazolato)]

AI-16a. Crystallographic data for 281

[(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)]

AI-16b. Data collection for [(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)] 281

AI-16c. Refinement parameters of 282

[(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)]

AI-16d. Selected geometric parameters (Å, º) for 282

[(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)]

AI-17a. Crystallographic data for 284

[(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)]

AI-17b. Data collection for [(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)] 284

AI-17c. Refinement parameters of 285

xxii

[(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)]

AI-17d. Selected geometric parameters (Å, º) for 285

[(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)]

AI-18a. Crystallographic data for 292

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

AI-18b. Data collection for (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene 292

AI-18c. Refinement parameters of 293

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

AI-18d. Selected geometric parameters (Å, º) for 293

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

AI-19a. Crystallographic data for 296

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AI-19b. Data collection for 296

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AI-19c. Refinement parameters of 297

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AI-19d. Selected geometric parameters (Å, º) for 297

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

AI-20a. Crystallographic data for 300

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AI-20b. Data collection for 300

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

xxiii

AI-20c. Refinement parameters of 301

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AI-20d. Selected geometric parameters (Å, º) for 301

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

AI-21a. Crystallographic data for (PPhMe2Au)LaBr2 304

AI-21b. Data collection for (PPhMe2Au)LaBr2 304

AI-21c. Refinement parameters of (PPhMe2Au)LaBr2 305

AI-21d. Selected geometric parameters (Å, º) for (PPhMe2Au)LaBr2 305

AI-22a. Crystallographic data for (PPhMe2Au)LaBr2 308

AI-22b. Data collection for (PPhMe2Au)LaBr2 308

AI-22c. Refinement parameters of (PPhMe2Au)LaBr2 309

AI-22d. Selected geometric parameters (Å, º) for (PPhMe2Au)LaBr2 309

AI-23a. Crystallographic data for (PPhMe2Au)LbBr2 312

AI-23b. Data collection for (PPhMe2Au)LbBr2 312

AI-23c. Refinement parameters of (PPhMe2Au)LbBr2 313

AI-23d. Selected geometric parameters (Å, º) for (PPhMe2Au)LbBr2 313

AI-24a. Crystallographic data for (PPhMe2Au)LcBr2 318

AI-24b. Data collection for (PPhMe2Au)LcBr2 318

AI-24c. Refinement parameters of (PPhMe2Au)LcBr2 319

AI-24d. Selected geometric parameters (Å, º) for (PPhMe2Au)LcBr2 319

AI-25a. Crystallographic data for Zn azadipyrromethene complex 322

AI-25b. Data collection for Zn azadipyrromethene complex 322

xxiv

AI-25c. Refinement parameters of Zn azadipyrromethene complex 323

AI-25d. Selected geometric parameters (Å, º) for 323

Zn azadipyrromethene complex

AI-26a. Crystallographic data for vanadyl azadipyrromethene complex 329

AI-26b. Data collection for vanadyl azadipyrromethene complex 329

AI-26c. Refinement parameters of vanadyl azadipyrromethene complex 330

AI-26d. Selected geometric parameters (Å, º) for vanadyl 330

azadipyrromethene complex

AI-27a. Crystallographic data for Mn azadipyrromethene complex 333

AI-27b. Data collection for Mn azadipyrromethene complex 333

AI-27c. Refinement parameters of Mn azadipyrromethene complex 334

AI-27d. Selected geometric parameters (Å, º) for 334

Mn azadipyrromethene complex

AI-28a. Crystallographic data for Fe azadipyrromethene complex 338

AI-28b. Data collection for Fe azadipyrromethene complex 338

AI-28c. Refinement parameters of Fe azadipyrromethene complex 339

AI-28d. Selected geometric parameters (Å, º) for 339

Fe azadipyrromethene complex

xxv

List of Boxes

Box Page

1.1.1. Lanthanide Contraction and Relativistic Effects 4

1.2.1. Criteria for Click Chemistry 11

1.3.1. Theoretical Requirements for Maximizing the 2PA 19

Cross-Section of a Chromophore

xxvi

Acknowledgements

First of all, I would like to thank Dr. Thomas Gray for his guidance and support, for giving me the opportunity to do various interesting research in his group.

Thanks to Dr. Dunbar, Dr. Protasiewicz, Dr. Sauvé, Dr. Burda and Dr. Berdis for sitting in my committee, and my former advisor, Professor Enbo Wang, for all the years’ support.

Thanks to the Gray and Protasiewicz group members. Thanks to Jim, Miya,

Marlena, Tom, Phoenix, Sam, Nihal and Ayan for being great colleagues and friends.

Special thanks to Jim and Nihal for doing all the X-ray crystallography data collections.

Thanks to the faculty and stuff of the chemistry department at Case Western

Reserve University, in particular, Dr. Dale Ray for all the help in NMR spectroscopy.

Thanks to Dr. Matthias Zeller from Youngstown State University for the help in

X-ray crystallography data collection, Mr. Tom Teets from Massachusetts Institute of

Technology for his help in emission lifetimes measurements.

Last but not least, I would like to thank both my Chinese and American families.

Without the love, understanding and support from my parents, my sister and my brother, I could never achieve what I have now. Thanks to my fiancé Jim and my

Updegraff parents, my life in America is not any more lonely, but full of surprises and love.

xxvii

List of Abbreviations a Length of unit cell axis (as in X-ray diffraction)

α Alpha angle (as in X-ray diffraction) between a and b axis

Å Angstrom

ABCN 1,1’-Azobis(cyclohexanecarbonitrile)

Ar Substituted aryl group b Length of unit cell axis (as in X-ray diffraction)

β Beta angle (as in X-ray diffraction) between a and c axis t-Bu tert-Butyl

Bpin 4,4,5,5-tetramethyl-1,3,2-dioxaborlyl

C Celsius c Length of unit cell axis (as in X-ray diffraction)

C6D6 Deuterobenzene

CDCl3 Deuterochloroform

CH2Cl2 Dichloromethane

CH3CN Acetonitrile cm-1 Reciprocal centimeters, wave numbers

CuAAC Copper-Catalyzed Cycloaddtion of Alkynes and Azides d Doublet (as in NMR spectroscopy)

δ Chemical shift (as in NMR spectroscopy)

Δ Heat (thermal reaction)

xxviii

DCM Dichloromethane dd Doublet of doublet (as in NMR spectroscopy)

Dx Density (as in X-ray diffraction)

E Entgegen (as in E, Z nomenclature)

ε epsilon (molar extinction coefficient in UV-Vis spectroscopy)

Eq Equivalents

ESI Electro-spray ionization (as in mass spectrometry)

Et Ethyl

F Structure factor (as in X-ray diffraction)

Fc Calculated structure factor (as in X-ray diffraction)

Fo Observed structure factor (as in X-ray diffraction) g Grams

γ Gamma angle (as in X-ray diffraction) between b and c axis h Hour, Miller indices (as in X-ray diffraction)

H3PO4 phosphoric acid

Hz Hertz

HOMO Highest occupied molecular orbital

HPLC High-pressure liquid chromatography

HWE Horner-Wadsworth-Emmons

HX Hydrogen Halides

J Coupling constant (as in NMR spectroscopy) in Hz

K Kelvin

xxix k Miller indices (as in X-ray diffraction) l Miller indices (as in X-ray diffraction)

L Ligand; liter

λmax lambda (wavelength of maximum adsorption in UV-Vis spectroscopy)

LUMO Lowest unoccupied molecular orbital

μ Mu

M metal, particularly Mo, W, or Re; molarity m multiplet (as in NMR) m/z mass-to-charge ration (as in mass spectrometry)

MALDI-TOF Matrix assisted laser desorption ionization-time of flight (as in mass

spectrometry)

Me Methyl

2-MeTHF 2-Methyltetrahydrofuran

MHz Megahertz mL Milliliters mm Millimeters

Mo Kα Molybdenum K alpha (as in X-ray diffraction) mol Mole mmol Millimole

Mr Molecular weight (as in X-ray diffraction) ms Millisecond

Mw Molecular weight

xxx

η Eta

N Normality

NBS N-bromosuccinimide

NHC N-Heterocyclic Carbene nm nanometer

NMR Nuclear Magnetic Resonance o Ortho

OMe Methoxy

ORTEP Oak Ridge Thermal Ellipsiod Plot

π Bonding pi orbital

π* Anti-bonding pi orbital

1PA One-Photon Absorption

2PA Two-Photon Absorption p Para

31P {H} proton-decoupled phosphorus NMR pd pseudo-doublet (as in NMR spectroscopy)

Ph- Phenyl

PPh3 Triphenylphosphine ppm Parts per million (as in NMR)

R Discrepancy index (as in X-ray diffraction)

Rf Retention factor (as in chromatography)

σ Bonding sigma orbital

xxxi

S Goodness of fit (as in X-ray diffraction) s Singlet (as in NMR spectroscopy); strong (as in IR spectroscopy)

T Temperature

TLC Thin-layer chromatography

Tmin Minimum transmission (as in X-ray diffraction)

Tmax Maximum transmission ( as in X-ray diffraction)

ω Omega (e.g, measurement angle used in X-ray diffraction)

θ Theta (e.g., Angle between the incident and the diffracted beams, as in

X-ray diffraction)

θmax Theta (e.g., maximum Bragg angle as in X-ray diffraction) t Triplet (as in NMR spectroscopy)

THF Tetrahydrofuran

TPA Two-Photon Absorption

UV-Vis Ultraviolet visible (as in spectroscopy)

V Cell volume (as in X-ray diffraction) in vacuo High vacuum manifold wR Weighted discrepancy index (as in X-ray diffraction)

X Cl, Br, or I ligand

Z Number of molecules in unit cell (as in X-ray diffraction); total nuclear

charge; zusammen (as in E, Z nomenclature)

xxxii

Functionalized Organogold(I) Complexes from Base-Promoted Auration,

Copper(I)-Catalyzed Huisgen 1,3-Dipolar Cycloaddition

and Horner-Wadsworth-Emmons Reactions

and

Metallo-Azadipyrromethene Complexes

for Solar Energy Conversion and Oxygen Evolution

Abstract

LEI GAO

Functionalized organogold(I) complexes were synthesized from base-promoted auration, copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition and

Horner-Wadsworth-Emmons reactions. The base-promoted auration process provides a mild and convenient way to generate Au–C bonds. Cu(I)-catalyzed cycloaddition produces 1,4-regiomeric products from benzyl azide and gold(I) internal alkynyls. The heavy atom effect of gold promotes the intersystem crossing. Triplet state emission is observed at room temperature for compounds with polycyclic substituents. These synthetic methods combined with modified Horner-Wadsworth-Emmons reactions produced two-photon absorbing gold(I) distyryl benzene and naphthalene complexes.

These compounds are strongly emissive, and the heavy atom effect of gold in potentiating the singlet oxygen generation is expected. Their two-photon absorption

xxxiii cross sections will be measured and compared. The optimal position of gold(I) installation, the number of gold(I) substituents and the geometry of the compound will be associated with their two-photon absorption cross sections and singlet oxygen generation efficiencies.

Gold(I) and gold(III) azadipyrromethene complexes were synthesized for solar energy conversion. Phosphinegold(I) azadipyrromethene complexes were synthesized and characterized. Synthesis of Au(III) complexes was attempted by reacting the azadipyrromethene ligands with Au(III) starting materials and directly reacting the phosphinegold(I) azadipyrromethene complexes with liquid bromine.

A tetradentate azadipyrromethene ligand was prepared and used to synthesize oxygen evolving metalloazadipyrromethene complexes. A zinc complex was synthesized to establish the structural and spectroscopic consequences of metal binding.

The absorption profile of the ligand carries over upon metalation. Weak emission is observed in the zinc complex. The binding geometry of the zinc centers confirms that the ligand can provide four coordination sites. A vanadyl complex was synthesized to study the compatibility of the ligand with metal oxos. The intact structure of the ligand upon binding to vanadyl proves that the ligand can support metal oxos without being oxidized. Afterwards, the reduced form of oxygen-evolving manganese and iron complexes were synthesized. Their oxos will be produced by reacting with oxygen-atom donors. The produced metal oxos will react with water, OH- as well as

OCl- to generate oxygen.

xxxiv

Chapter 1. General Introduction

1.1. The Chemistry of Gold

Gold, to most people, a noble metal with a metallic yellow color and glittering appearance, has been one of the most popular materials to make coins, medals and jewelries. Considered as a symbol of wealth and power, it appears almost everywhere in most cultural stories.1-3 Gold metal has high resistance to most corrosive forces. For at least three millennia, it has been considered as “King of the Metals”. Only a few powerful oxidants, such as aqua regia, chlorine, and bromine can dissolve gold.4

In the 19th and 20th century, gold chemistry distinct from the alchemy of the last millennium was finally established. The “not-so-noble” nature of gold started to emerge. The element gold has the atomic number of Z = 79. It has the electronic ground state configuration of [Xe][4f14][5d10][6s1]. This makes gold(I) with a closed-shell configuration [5d10] prevail in gold compounds. Interestingly, when reacting with highly oxidizing reagents, gold(III) and even gold(V) compounds can be generated. These high oxidation states are unusually difficult to access for the other two coinage metals, copper and silver. Au-, known as auride anion, also exists in many stable compounds, such as Cs+Au-.5

In organometallic chemistry, gold(I) and gold(III) complexes are the most intensively studied. Gold(I) complexes are generally found in a linear geometry with two donor atoms. The ligands can be neutral (L) or anionic (X-), and the general

gold(I) compounds usually take the form of [L–Au–L] or [X–Au–X]-/[L–Au–L]+. Tri- and tetracoordinated gold(I) complexes also exist, but in a relatively small number.

These compounds are usually strongly distorted, with the last incoming ligands at longer distances from the metal center.6 This is because the two- and three- coordinate gold(I) substrates are very poor acceptors. Comparatively, most copper(I) compounds are tetra- or tri-coordinated, and linear two coordinate Cu(I) complexes are relatively rare. The most prevalent coordination number for silver(I) is 4, with 2 and 3 also abundant.7 The distribution of the coordination numbers for crystal structures of CuI,

AgI, and AuI compounds found in the Cambridge Structural Database by 2004 is plotted as shown in Figure 1.1.1.7

Figure 1.1.1. Distribution of the Crystal Structures of CuI, AgI, and AuI Compounds According to Coordination Number of the Metal Atom as Found in the Cambridge Structural Database.7 (Reprinted from ref. 7, with permission from the American Chemical Society.)

Au(III) with a 5d8 electron configuration requires square planar tetracoordination, which is analogous to its isoelectronic metal cations Pt2+ (5d8), and

Ni2+ (3d8) in the 3d block. There are very few mononuclear gold(II) compounds.

Au(II) usually occurs in dinuclear and diamagnetic compounds with a pair of tightly

4+ bonded gold atoms in a [Au2] unit. The Au(II) atom is also square-planar

and the second Au(II) acts as one of the ligands.8-10 Another kind of Au(II) compounds are mixed-valent compounds with equimolar Au+ and Au3+. Au(V) with a

5d6 electron configuration usually binds ligands in an octahedral geometry, analogous to Pt4+(5d6) and Fe3+ (3d6). These complexes are rare and restricted to complexes with

- 11 fluoride ligands as in AuF5 and [AuF6] . Shown in Scheme 1.1.1 are the coordination patterns of different gold centers.

Scheme 1.1.1. Coordination Patterns of Different Gold Centers.

Cationic Au(I), Au(III), as well as rare Au(II) species are strong Lewis acids.

They have high affinity to nucleophiles, and can even bind the rare, noble gas xenon in their first coordination sphere.12, 13

Most of the unusual properties of gold can be explained based on a combination of “lanthanide contraction” and the “relativistic effects”, Box 1.1.1. The lanthanide contraction partially explains the relatively small radius of the gold atom, but it cannot explain why the element gold has the maximum redox potential and electron affinity relative to the other elements with atomic numbers Z = 72-83. The relativistic s-orbital contraction and d-orbital expansion are very obvious when taking the

relativistic effects into account. The increase of the ionization energy and electron affinity can be explained as related to the 6s configuration.14 As shown in Figure

1.1.2, the calculated relativistic contraction of the 6s orbital reaches a maximum at

Au.15, 16 This explains why gold(I) is much smaller than silver(I). Actually, the gold(I) radius falls between copper and silver.17, 18

Lanthanide Contraction. The decrease in ionic radii of the elements in the lanthanide

series from atomic number 58, Cerium to 71, Lutetium, which results in smaller than otherwise expected ionic radii for the subsequent elements starting with 72, Hafnium.

Relativistic Effects. When the velocity of a body approaches light speed, its mass

increases, which can be expressed mathematically as 1 . For a given

atom, the average radial velocity of the s electron is Vr = Z, with Z being the atomic number. Light speed c equals 137 a.u. (atomic unit). The Bohr radius of an electron is inversely proportional to its mass. As a result, the relativistic radius of 6s electron

1 In Au, Z = 79 and v/c for the 6s electrons is 79/137 = 0.58. As a

result, r = 0.81 r0. This effect applies to s and p orbitals. This explains the high ionization energy of the 6s electron of Au.

Box 1.1.1. Lanthanide Contraction and Relativistic Effects.

0.98

0.96

0.94 79Au

0.92

r  /r  R NR 0.9

0.88

0.86

0.84

0.82 60 70 80 90 100 Z

Figure 1.1.2. Calculated Relativistic Contraction of the 6s orbital.15, 16

Based on this theory, the yellow color of bulk gold can be ascribed to a small band gap between the full 5d orbitals (expanded) and the Fermi level of the half-filled

6s orbital (contracted). This separation would be much larger if no relativistic effects were taken into account.19, 20 The readily available higher oxidation states of gold can also be explained based on the relativistic effects. The expansion of the 5d orbitals and the contraction of 6s orbital lower their energy gaps, and modify the spin-orbit coupling effects. Hybrid orbitals which can support square planar and octahedral configurations allow for the formation of gold complexes in high oxidation states, which are more energetically favorable than in the most common +1 oxidation state.

Currently, (phosphine)- and (N-heterocyclic carbine)gold(I) species are intensively studied. These cations are isolobal with the proton,21 and they bind terminally to aromatic carbon much like hydrogen and halogens. Unlike H+, they are soft Lewis acids, and their Lewis acidity is partly ascribable to the relativistic contraction of the 6s orbital,19, 22, 23 which dominates bonding in a two-coordinate linear geometry.24 Lately, synthesis of compounds with the relativistic LAu+ fragments has gained recognition in organometallic chemistry.25-28 The heavy atom effect of gold29-35 and its perturbation in spin-orbit coupling has induced interesting ground and excited-states properties. The spin-orbit coupling constant of 5d-electrons in gold is 5090 cm-1,36 and that of a 5p electron in iodine is 5700 cm-1.37 Upon attaching a LAu+ fragment to the periphery of a polycyclic organic skeleton, efficient

intersystem crossing leads to triplet-state emission which is unobservable in the free ligand at room temperature.25, 38

When the steric hindrance of the substitution ligands is not important, Au(I) centers can approach each other to form bonds with energy close to hydrogen bonding, 7-11 kcal/mol.39-41 The strong interaction is sufficiently strong to persist in solution and play a role in guiding chemical reactions.42 The Au–Au distances are typically 2.8–3.3 Å, well below the sum of the van der Waals radii (ca. 3.6 Å). This interaction is termed “aurophilic interaction”. It not only happens in neutral complexes, but also in cationic and anionic complexes where Coulombic factors would be expected to cause significant repulsion.43 Shown in Scheme 1.1.2 are typical interaction patterns which lead to the formation of Au–Au dimers.

Scheme 1.1.2. Aurophilic Interaction in L–Au–L Dimers.

The aurophilic interaction can also lead to the formation of trimers, tetramers, one-dimensional chains or even two-dimensional layers and three-dimensional networks. These supermolecular networks build up with monomers associated simply by Au–Au contacts. The bond strengths can vary in one polymeric system, and various solid structures can be generated. Many gold(I) complexes with aurophilic interaction exhibit strong luminescence. It is proposed that the aurophilic interaction

stabilizes the excited states. The change of the environment,42, 44, 45 such as concentrations, solvents, different counter-ions, the incorporation of solvate molecules46, 47 and even grinding48 in the solid state, which can modify the aurophilic interactions also induces different luminescence patterns. Not only can this aurophilic interaction happen intermolecularly, intramolecular aurophilicity is also very common. Multinuclear gold(I) complexes with the form of XAun (n = 2–6) have been reported.49 These complexes can be tetrahedral,50 square-pyramidal,51 trigonal-bipyramidal,51 and octahedral.52, 53 Upon increasing the number of Au(I) centers, the Au–X–Au angles decrease, and the gold atoms would form the shortest possible intermetallic distances.49 Numerous theoretical calculations have been done to study the fundamental causes of aurophilic interactions.19, 54-57 It has been shown that attractive aurophilic interactions are caused by a combination of correlation effects and relativistic effects.19

The unique properties of gold have initiated great research interest ranging from nanomaterials58-61 to catalysis62-69 and from cancer treatment70-72 to energy recovery.73-75 Material chemistry related to gold is generally focused on gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles. The behavior of individual particles, their size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology position AuNPs as key materials in the 21st century.58

Lewis acidic cationic phosphine-gold(I) complexes can act as catalyst in hydration of alkynes,76 C–C bond forming reactions,77, 78 hydroarylation reactions,79-81 and several carbon-heteroatom bond-forming reactions.82-84 Tuning the ancillary ligands, such as using more electron-withdrawing phosphine [(4-CF3-C6H4)3P],

Buchwald-type ligands, or N-heterocyclic carbene(NHC) ligands can enhance the catalytic efficiency towards certain reactions, such as ring expansion of propargylcyclopropanols,85 intramolecular hydroamination of allenes,86 and indene

87 synthesis, respectively. Multinuclear complexes, such as trimeric (PPh3Au)3OBF4, were proved to be superior to monomeric Au phosphines as a catalyst for the propargyl Claisen rearrangement.88 In some cases, gold nanoparticles show excellent catalytic activity for Suziki-Miyaura cross-coupling reactions in water.89 Au(III) complexes are good catalysts for intramolecular and intermolecular addition of nucleophiles to alkynes.90-94 However, because of stability issue with Au(III) complexes,95, 96 most efforts have focused on Au(I).

Research concerning the antitumor activity of phosphine Au(I) species has been on-going since 1980s.97, 98 These Au(I) complexes are divided into three distinct classes based on their difference in targeting mitochondrial functions. They are neutral linear two-coordinate Au(I) complexes such as Et3PAuCl and tetraacetylthioglucose gold(I) phosphine complex (auranofin), and cationic tetrahedral

+ bis-chelated Au(I) phosphine complexes such as [Au(dppe)2] , Scheme 1.1.3.

Scheme 1.1.3. Examples of Au(I) Phosphine Antitumor Complexes.

Auranofin (trade name Ridaura) is an orally administered anti-arthritic gold drug.

It has been observed that auranofin can inhibit the growth of cultured tumor cells in vitro. Mechanistic studies have shown that auranofin induces apoptosis by inhibiting the mitochondrial enzyme thioredoxin reductase (TrxR),99, 100 which has recently become a new target for drug development. The antitumor activity of the tetrahedral

+ Au(I) diphosphine complexes with the common form of [Au(dppe)2] was first reported two decades ago.97, 101 The activity is considered to be coming from their lipophilic, cationic properties which can lead to their accumulation in mitochondria.

Substituting the phosphine ligands with N-heterocyclic carbenes allow for a generation of drugs with tunable dydrophilic/lipophilic properties.97, 102 Square-planar

Au(III) complexes are also investigated for antitumor activities. They are isoelectronic and isostructural with square planar Pt(II) complexes, and may form similar DNA adducts.101 However, Au(III) complexes can readily decompose into

Au(I) under physiological conditions. Appropriate choice of ligands to stabilize the

Au(III) oxidation state is important.103, 104

The two common stable oxidation states of gold, Au(I) and Au(III), are a very good pair in an oxidation addition/reductive elimination cycle. Recently, Nocera and coworkers reported the halogen photoreductive elimination from gold(III) centers.75

Upon LMCT excitation of solutions of monomeric complexes of the type

III I,III Au (PR3)X3 and bimetallic complexes of the type Au2 [μ-CH2(R2P)2]X4 and

III,III - - III Au2 {μ-CH2(R2P)2}X6 (R = Ph, Cy, X = Cl , Br ), the Au –X bonds are activated.

III Unprecedented two-electron photoelimination of X2 from a monomeric Au center and four-electron photoelimination of X2 from a bimetallic center are observed. The quantum yields of X2 photoproduction are between 10% and 20%. These photochemical reactions proceed smoothly in the solid state. Efficient X2 photoelimination is observed without a chemical trap, making the solid state photoinduced elimination of halogen an energy-storing photoreaction. The concept of storing solar energy in chemical bonds is realized in the AuIII/AuI pair.

1.2. Copper(I)-Catalyzed Click Chemistry of Huisgen Azide-Alkyne 1,3-Dipolar

Cycloaddition

In 2001, Sharpless introduced a chemical philosophy, named “Click

Chemistry”.105 It describes chemistry tailored to generate substances quickly and

reliably by uniting small units together. Reactions that can be considered as “Click”

have to meet stringent criteria,105 Box 1.2.1. Few reactions satisfy these strict

requirements. They are nucleophilic ring-opening reactions of strained rings such as

epoxides and zairidines, non-aldol carbonyl chemistry, and certain classes of

addition to carbon-carbon multiple bonds.

CLICK CHEMISTRY

Click Chemical Reactions are...

 Modular, wide-scope reactions  Very high yielding  Stereospecific

Click Chemical Reactions Require…

 Readily Available Reagents  Inoffensive byproducts, if any; purification is non-chromatographic  Simple reaction conditions (ideally insensitive to O2 and H2O)  No solvent or one that is benign and easily removed  Simple (non-chromatographic) product isolation

Box 1.2.1. Criteria for Click Chemistry. Adapted from Ref. 104.

However, the prototype of click chemistry is the copper-catalyzed Huisgen reaction, the 1,3-cycloaddition of azides to terminal alkynes, Scheme 1.2.1. The

Huisgen 1,3-dipolar cycloadditions106 are exergonic fusion processes in which two unsaturated reactants are united to produce a variety of five-membered heterocycles.

The 1,3-dipolar cycloaddition reaction between acetylenes and azides to make triazoles was introduced by Huisgen as early as 1960.106 The pioneering work was mainly focused on conducting the reactions without catalysts at elevated temperatures in the absence of water. In 2001, Tornøe and Meldal introduced Cu(I) into the cycloaddition of organic azide and alkynes.107 Great improvements in both rate and regioselectivity discovered by Meldal and Sharpless laboratories led to a revolution in material design and synthesis.108, 109

Scheme 1.2.1. Cu(I) Catalyzed 1,3-Dipolar Huisgen Cycloaddition.

The Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC) reactions are virtually quantitative, very robust, insensitive, general and ligand orthogonal. They have been used to modify peptides, natural products, and pharmaceuticals.110 A large number of modified nucleosides and oligonucleotides have been synthesized.111 In materials science, CuAAC has been used to generate linkers for the assembly of large fragments and even for the synthesis of long linear polymers.112 Typically, a core perylenediimide was linked by triazole coupling to four antennae containing

BODIPY, generating an efficient light harvesting molecule.113 CuAAC also provides an efficient way to modify surfaces, such as polystyrene, polyethylene, glass, silica,

silica gels and gold. Virtually any material, to which an alkyne or azide can be attached, may be functionalized by CuAAC.114

CuAAC provides 1,4-disubstituted triazoles. The recently identified ruthenium(II) based catalysts, such as (pentamethylcyclopentadienyl)ruthenium(II), lead to wholly or predominately 1,5-triazolate isomers.115-117 The ruthenium-catalyzed variant produces triazolates from unstrained internal alkynes. However, most of copper-catalyzed [3+2] cycloadditions work essentially on terminal organic acetylenes. The only two exceptions thus far is the copper(I) catalyzed cycloaddition of benzyl azide and a symmetric alkyne, 2-hexyne.118, 119

Copper(I) salts, such as CuI and CuBr, and coordination complexes, such as

109 120 121, 122 [Cu(CH3CN)4]PF6, (Et3O)3P·CuI and [Cu(PPh3)3]Br can be used directly in the cycloaddition reactions. Coordination Cu(I) complexes are advantageous in organic solvents in which inorganic Cu(I) salts have limited solubility. However,

Cu(I) is thermodynamically unstable and can be easily oxidized to Cu(II), which is catalytically inactive. A combination of Cu(II) salts, such as Cu(OAc)2 and

CuSO4·5H2O, with a sacrificial reducing agent, for example, ascorbate, can be used as a very good alternative.109 Catalytic amount of Cu(I) can also be introduced to the reaction through comproportionation of Cu(II) and Cu(0).109, 123 By adding a small piece of copper metal to the reaction mixture, the copper oxides and carbonates (the patina) present on the surface will be enough to initiate the catalytic cycle. To make it more efficient, the catalyst can be introduced as copper nanoclusters, or 13

copper/cuprous oxide nanoparticles. Although longer reaction time is always required, it usually yields very pure products with low level of copper contamination.124, 125

The catalytic activity and stability of copper catalysts can be affected by ligands.

For example, tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA) discovered soon after the disclosure of CuAAC, significantly accelerates the CuAAC reaction and stabilizes the +1 oxidation state of the copper catalyst.126 Additionally, its ability to sequester copper ions can prevent damage to the biological molecules in biological synthesis. A dicopper-substituted γ-Keggin silicotungstate

TBA4[γ-H2SiW10O36Cu2(μ-1,1-N3)2] (TBA = tetra-n-butylammonium)silicotungstate shows superior catalytic activity in large-scale cycloaddition of benzyl azide to phenylacetylene under solvent-free conditions.127 In addition, it can be used in the one-pot synthesis of 1-benzyl-4-phenyl-1H-1,2,3-triazole from benzyl chloride, sodium azide, and phenylacetylene. The successful cycloaddition of an internal alkyne, 2-hexyne, with benzyl azide was realized by using a copper(I) complex

[Cu(C186tren)]Br (C186tren = tris(2-dioctadecylaminoethyl)amine) and

N-heterocyclic carbene substituted copper(I) complexes, respectively.118, 128

The catalytic role of copper in the triazole formation has generated and is still inviting a lot of disputes and revisions.110 The most common idea is that the copper(I) species forms a π complex with the triple bond of a terminal alkyne, Step A, Scheme

1.2.2. This coordination is calculated to move the pKa of the alkyne terminal proton down by ca. 10 units, making it possible to be deprotonated in an aqueous medium. 14

The azide is then activated by coordinating to this copper center (Step B). The intermediate formed in this step is converted to an unusual 6-membered copper metallocycle (Step C). This is the key bond-forming step, which is endothermic by

12.6 kcal/mol with a calculated barrier of 18.7 kcal/mol, much lower than the barrier for the uncatalyzed reaction (approximately 26.0 kcal/mol). This step accounts for the enormous rate acceleration by Cu(I). Afterwards, the copper metallocycle undergoes ring contraction to give the triazolyl-copper derivative (Step D), which undergoes proteolysis to release the triazole (Step E), thus completing the catalytic cycle.129

N N N R2

R1 H R1 H [CuLx]

+ Step E Step A H H+

N R2 NN R1 CuLx

R1 CuLx NN N R2

Step D Step B

N N N R2 R2 N N N

CuLx R1 CuLx R1 Step C

Scheme 1.2.2. Proposed Catalytic Cycle for CuAAC. Adapted from Ref. 129.

1.3. Two-Photon Absorbing Chromophores

Two photon absorption (TPA) is a phenomenon in which the same molecule absorbs two photons of identical or different frequencies simultaneously to reach the excited state. It was theoretically predicted by Göppert-Mayer in 1930s.130 Thirty years later, the invention of laser permitted the first experimental verification of this phenomenon. Two photon excited fluorescence was first observed in a europium-doped crystal,131 and then in cesium vapor.132 Currently, the most popularly used techniques for measuring 2PA are z-scan and two-photon excited fluorescence.

The z-scan is very useful for probing nonlinear transmission and for characterizing nonlinear refraction. The TPEF intensity provides direct information on the efficiency of TPA. Only a dilute solution is necessary.

One-photon absorption (1PA) is linearly dependent on the light intensity.

Two-photon absorption (2PA) involves simultaneous interaction of two photons, thus increases with the square of the light intensity. This explains why only particularly focused pulsed lasers which can generate very high instantaneous photon intensity can detect 2PA. Requiring photons of half the energy (or twice the wavelength) of the corresponding one-photon transition to access the excited states, 2PA reveals its wide applications in microscopy,133, 134 microfabrication,135 three-dimension data-storage,136, 137 optical power limiting,138 up-converted lasing,139 photodynamic therapy,140 and localized bio-active species release.141

“Cross-section” is used to quantify the efficiency of 2PA. It is usually denoted as

δ and measured in Göppert-Mayer units (1 GM = 10-50 cm4 s photons-1 molecule-1).

The calculation of δ is based on assumptions equivalent to those of the Beer-Lambert law for 1PA. Its function is like the absorption coefficient for 1PA. Shown in Figure

1.3.1 are the equations used in the theoretical calculations, and Figure 1.3.2 is the diagram based on the essential state models.

I 2 NI2  NFI (1) z I F  (2) h 21hL4  max  222S fg (3)  0 nc  2 22 gi if1    gi gf   gi if S fg  (4) ()5Eh h () Eh 2 iifggi ,  gi

D Term T Term I :intensity F : photon flux

 2: molecular cofficent for 2PA : 2PA cross section : half-with at half-maximum of the 2PA band in energy units

Egi : energy gap between the ground state and an intermediate state i

kl : amplitude of the oscillating (transition) dipole moment (or polarization) induced by the electric field of a light wave whose frequency matches (is in resonance with) the energy difference between the kl and states

Figure 1.3.1. Equations for the 2PA Cross Section Calculation.142

As shown in Figure 1.3.2, in a centrosymmetric molecule, the three essential states have alternating symmetry. The ground state and the final excited state are symmetric with respect to the center of inversion (gerade), whereas the intermediate state is antisymmetric (ungerade). In 2PA, the photon frequency ν is out of resonance with both of these transitions. However, when the molecule experiences the field of

the first photon, a “virtual state” which is a superposition of ground state and the intermediate state is induced. The ungerade parity in this state allows the second photon at frequency ν to induce an electric-dipole transition to the final gerade state.

As a result, the 1Ag↔2Ag which is not allowed in 1PA now is allowed in 2PA. This reversal in selection rules between 1PA and 2PA is general to all centrosymmetric chromphores. In non-centrosymmetric molecules, the g↔f transition is electric-dipole allowed, and appears in both 1PA and 2PA.

(a) Centrosymmetric (b) Non-Centrosymmetric Chromophore Chromophore

Final State f 2Ag f 2A

h h Intermediate State i 1B1u

Virtual State

Egi h h

Ground State 1A g 1Ag g

Figure 1.3.2. Energy Level Diagrams for the Essential States in (a) centrosymmetric and (b) non-centrosymmetric chromophores. The States are labeled for D2h and C2 symmetry, respectively, but the diagram is general to the lowest 2PA transition in any centrosymmetric or non-centrosymmetric molecules.142

In equation 4, all static dipole moments are zero and the D term is absent when the molecule is centrosymmetric. The 2PA cross-section can be calculated based on the simplified equation shown in equation 5.

22 gi if max  C 2 (5) Eh/1  gi

In non-centrosymmetric molecules, the D term is not zero. The T term only has a small contribution in dipolar chromophores, and the D term here is intrinsically smaller than the T term for centrosymmetric systems. This partially explains why most dipolar 2PA chromophores have smaller cross-sections than comparable quadrupolar analogues.

2 2 μgi and μgf in these equations can be calculated based on linear absorption spectra because they are proportional to the one photon oscillator strengths. However, μif is rarely determined experimentally. This makes the design of efficient 2PA chromophores rely on theoretical calculations.

Requirements for Maximizing the 2PA Cross-Section of a Chromophore

1. Long, π-conjugated chains with enforced coplanarity that ensure large

conjugation lengths (leads to high values of μgi, μif, μgf and /or Δμgf 2. Donor and acceptor groups at the center and ends of the molecule that can

also enhance μgi, μif, μgf and /or Δμgf 3. Centrosymmetric chromophores with strong 1PA transition close to the 2PA

laser wavelength. δ values enhance when the Δ value is small [Δ = Egi-hν]; if Δ = 0, 2PA will be difficult to observe because of overlap with the 1PA.

4. Chromophores with narrow one- and two-photon absorption bands. A

narrow 2PA band (small Γ) leads directly to a high δmax value because the

area of a 2PA band is fixed by the Sfg value (equations 3 and 4). In centrosymmetric molecules, the requirement for the intermediate state to be close to, but not overlapping with the virtual state needs a sharp 1PA band.

Box 1.3.1. Theoretical Requirements for Maximizing the 2PA Cross-Section of a Chromophore.142

Shown in Box 1.3.1 are the conclusions based on theoretical studies. Commonly, conjugated chromophores with an electron donor D and an electron acceptor A at the ends (D–π–A system), and centrosymmetric chromophores with D–π–A–D or

A–π–D–A structures tend to have large cross sections.143, 144

Extensive research is being carried out to develop efficient two-photon absorbing chromophores. Although a few dipolar systems with rather high 2PA cross-sections have been reported,145, 146 centrosymmetric dyes are more intensively studied because dipolar systems generally give weaker 2PA than centrosymmetric chromophores of the same size and complexity. Both linear and two-dimensional centrosymmetric dyes have been reported. The design of linear centrosymmetric dyes is based on the choice of terminal groups, as well as the length of the π system and the conformation of the central bridges and cores.

In 1997, Marder, Perry and co-workers have found that by attaching terminal donor substitutents to trans-stilbene, the 2PA cross-section is enhanced almost ten times.147 Afterwards, attaching two donor (D) or two acceptor (A) terminals to a conjugated system becomes a general approach to design 2PA chromophores. The most widely used terminal donor groups are dialkyl and diaryl amino groups,148, 149 and many π-deficient heterocycles are used as electron-accepting terminal groups.143,

148 It has been concluded that D–π–D and D–π–A–π–D systems tend to be more effective than A–π–A and A–π–D–π–A systems. Modifying the central core by attaching electron-withdrawing groups usually enhance 2PA.148 20

If no electron delocalization is involved when linking two chromophores

together, the 2PA will simply double (δ  Ne). When the π systems are strongly coupled, 2PA cross-section will increase more strongly because of the increase in the transition dipole moments μig and μif. However, this does not mean that the longer the molecule is, the more efficient 2PA is. δ/Ne is usually used to compare the 2PA efficiency of chromophores with different number of π electrons. This ratio will saturate as the length of the molecule exceeds the π-delocalization length.150

2PA efficiency can also be enhanced by restricting the free rotation of the conjugated systems to acquire a planar geometry, thus maximizing π-orbital overlap.148,151 Ethynylene linkers usually provide less conjugation152 than vinylene groups because there are π–π and π*–π* energy mismatches at C(sp1)–C(sp2) connections, and the alteration of the bond length is greater. When steric congestion is an issue, the acetylenic systems tend to be more conjugated because the acetylene cannot twist out of conjugation,153-155 thus increasing the efficiency of 2PA.

Large, π-conjugated macrocycles, such as porphyrins, are very good two-photon absorbers.145, 156, 157 Two-dimensionally extended porphyrins,158, 159 heteroporphyrins,160 and other porphyrin analogues161-163 also display strong 2PA.

Other two-dimensional 2PA chromophores include recently designed cyclic oligothiophene macrocycles,164 branched planar chromophores with electron-deficient triazine cores,165 annulenes,166 and acetylene-linked dendrimers.167

1.4. Azadipyrromethenes

Azadipyrromethenes, compounds of type 1 in Figure 1.4.1, are a series of chromophores first described in the 1940s.168-170 Since then, these chromophores remained unstudied for their applications until 2004 when O’Shea’s group used BF2 adducts of tetraarylazadipyrromethenes (compounds of type 2 in Figure 1.4.1) as efficient singlet oxygen generators for photodynamic therapy.171

Figure 1.4.1. Core Structures of Azadipyrromethenes.

The BF2 chelates of azadipyrromethenes are analogs of intensively studied

BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) dyes.172 BODIPY dyes, as shown in Figure 1.4.2 along with the corresponding dipyrromethene and their saturated version, dipyrromethane, are strong UV lights absorbers, and emit with relatively sharp fluorescence peaks in high quantum yields. Due to their good stability upon polarity and pH change of the environment, the BODIPY dyes are widely used to label proteins and DNA.173-178

Azadipyrromethenes share similar characteristics with dipyrromethenes, such as their stability upon environment change, tunable absorption and emission features by

+ changing substitutents, and good chelating properties for not only BF2 fragments, but also many metal centers.172

Figure 1.4.2. Core Structures of BODIPY, dipyrromethenes and dipyrromethanes with their numbering systems.172

There are generally two methods available to synthesize azadipyrromethenes,168-171 shown in Scheme 1.4.1. In one method, 2,4-diarylpyrroles are converted to their 5-nitroso derivatives, and then condensed with a second molecule of pyrrole, Scheme 1.4.1a. In the second method, a Michael addition of chalcones with nitromethane or cyanide is first performed to generate A or B

(Scheme 1.4.1b). A or B is then further reacted with formamide (or other ammonia sources) to form the azadipyrromethene cores (Scheme 1.4.1c and Scheme 1.4.1d).

Initially, these reactions were carried out without solvent. Later on, O’Shea and coworkers found out refluxing the reaction mixture in alcohol solvents can lead to the precipitation of azadipyrromethenes. This modified procedure usually gives higher yields and makes the isolation much easier. The synthesis tends to be most facile when there are four phenyl substitutents. Successful synthesis of azadipyrromethenes with other substitutents requires modifications of the reaction procedures. Typically,

unsymmetrical azadipyrromethenes are synthesized using the method shown in

Scheme 1.4.1a. Attaching up to four different aryl substituents on the azadipyrromethene has been realized using a stepwise route.179 Some unsymmetrical and most symmetrical azadipyrromethenes were made based on Scheme 1.4.1b, c and d.172

Scheme 1.4.1. Synthetic Pathways for Azadipyrromethenes.172 (a) from nitroso pyrrole; (b) nitrobutyrophenones A and keto-nitrile B; (c) proposed mechanism for the formation of azadipyrromethene from nitrobutyrophenones A; (d) from keto-nitrile B.

Usually, the synthesized azadipyrromethenes are transformed into their BF2 chelates (Aza-BODIPY) which are further used as chemical sensors. They have strong and sharp absorption in both UV and NIR regions, and the extinction coefficients range from 75 000 to 85 000 M-1cm-1, which is much greater than substituted porphyrins (3000–5000 M-1cm-1).172 Besides being used as efficient singlet oxygen generators in photodynamic therapy,171 compounds of type 1 in Figure 1.4.3 are attached to polystyrene beads, and the composite turned out to have excellent photophysical properties, and can act as off/on sensors.180 B, O-chelated azadipyrromethenes,181 type 2 compounds in Figure 1.4.3, emit between 740 nm and

780 nm and are synthesized as NIR probes. Compound 3 with amine substituents is a

“triple absorption and emission responsive sensor”.182 Dramatic pH responsive absorption and fluorescence changes can be observed across a broad acidity range, which is accompanied by a visible colorimetric change from red to purple to blue. An aza-BODIPY-18-crown-6 ether complex183 (compound 4 in Figure 1.4.3) is an excellent visible chemosensor for the marine toxin saxitoxin, which is the most toxic component of paralytic shellfish poisons. Compound 5 with a well-defined “pocket” provided by two 2-pyridyl substituents proved to be a selective chemosensor for

Hg(II) ions.184 Constrained azadipyrromethenes, like compound 6 in Figure 1.4.3 were also synthesized. These compounds usually absorb at longer wavelengths compared with “non-constrained” azadipyrromethenes. They have excellent chemical and photo-stability, and their fluorescence is insensitive to solvent polarity.185, 186

With a number of different azadipyrromethene core structures available, substitution chemistry with various functional groups can be performed, and the azadipyrromethene system can be delicately functionalized. Scheme 1.4.2 shows an example. By refluxing a THF solution of compound a with propargyltosylate and

NaH, one or two OH groups can be alkylated. The generated alkynyl (compound b) further undergoes copper(I) catalyzed cycloaddition with azide to form a triazolate-functionalized azadipyrromethene (compound c). This compound can be used as a pH responsive NIR fluorescent imaging probe.187

Figur 1.4.3. Functionalized Azadipyrromethenes.

Scheme 1.4.2. Functionalizing Aza-BODIPY with Copper(I) Catalyzed 1,3-Dipolar Alkyne-Azide Cycloaddition. 26

Research efforts were also devoted to substitute the two pyrrolic protons with bromides. Br2 was usually used as the bromination reagent. The brominated

+ azadipyrromethenes occur as a hydrobromide salt. The BF2 chelates of these brominated azadipyrromethenes show significant decrease in fluorescence quantum yields and increased singlet oxygen production, indicating a larger heavy-atom effect brought about by the Br substituents.171

+ Besides BF2 , azadipyrromethenes can also readily bind metal ions.

Three-coordinate azadipyrromethene complexes of copper(I), silver(I) and gold(I) were first prepared by reacting phosphine copper(I), silver(I) and gold(I) with azadipyrromethenes deprotonated by a properly chosen base.188, 189 Meanwhile, homoleptic, four-coordinate azadipyrromethene complexes of d10 Zn(II) and Hg(II) complexes were synthesized by simply stirring a THF solution of Zn(OAc)2 or

190 Hg(OAc)2 with two equivalents of azadipyrromethene. The Zn(II) and Hg(II) centers coordinate to four nitrogens from two individual azadipyrromethene molecules, adopting a pseudotetrahedral geometry, with a significant distortion from

D2d symmetry. Later on, O’Shea’s group reported the synthesis of tetraphenylazadipyrromethene Co(II), Ni(II), Cu(II), and Zn(II) complexes by refluxing the acetate salts with tetraphenylazadipyrromethene in butanol.191 The strong absorption of the ligands is carried over upon chelating to metals centers. The three-coordinate phosphine Cu(I), Ag(I) and Au(I) azadipyrromethene complexes are luminescent, but with very low quantum yields. The other four-coordinate Co(II),

Ni(II), Cu(II), Zn(II) and Hg(II) complexes are considered as non-luminescent.

Recently, Gray’s group reported the synthesis of fac-tricarbonyl rhenium(I) azadipyrromethene complexes.192 Both the ligand and the metallo-complexes undergo reductive electrochemistry. A second reduction event that is reversible for the free ligand is irreversible in metallo-complexes, likely indicating participation of the

+ fac-[Re(CO)3(L)] moiety. Figure 1.4.4 shows the structures of these metal complexes.

Figure 1.4.4. Reported Metallo-Azadipyrromethene Complexes.

1.5. Proposed Research

Described here are research projects including attaching gold(I) to different ligand skeleton systems to pursue different properties, and metallo-azadipyrromethene complexes for solar energy conversion and O2 evolution.

A. Base-Promoted Au–C Bond Formation38

Traditional Au–C formation involves pyrophoric reagents.193 An organic halide

(usually an aryl halide) is first treated with n-butyllithium to make a n-butyllithium salt. Au–C bond is formed after reacting this salt with a gold(I) starting material.

Grignard reagents can also be used. A halide is treated with Mg in THF and then reacted with gold(I) starting materials to accomplish the Au–C formation. However, organic skeletons bearing nitro, aldehyde, ketone, and ester groups cannot survive the n-butyllithium or Grignard process. Meanwhile, if these reactions are not handled well (such as excess n-butyllithium is introduced into the system), decomposition of gold(I) into gold nanoparticles may become a big issue. In this chapter, a mild base-promoted tramsmetalation process is used to attach gold(I) fragments to the periphery of naphthalene. This process is simple, and can tolerate various functional groups. Shown in Scheme 1.5.1 is the synthesis of a digold(I) naphthalene complex.

Scheme 1.5.1. Au–C Formation from Base-Promoted Auration. 29

Commercially available naphthalene boronic acids will be used. Naphthalene boronate esters which are not commercially available will be synthesized based on literature procedures. All the new gold(I) naphthyl complexes will be fully characterized by multi-nuclear NMR (31P{1H}, 1H and 13C{1H} when necessary),

UV-vis and fluorescence spectroscopy, Mass spectrometry, elemental analysis and

X-ray crystallography when diffraction-quality single crystals are available. The photophysical properties of these complexes will be discussed concerning the heavy atom effect of gold.

B. Cu(I) Catalyzed Au(I) Click Chemistry194, 195

The Cu(I) catalyzed Huisgen 1,3-dipolar cycloaddition of alkynes and azides mostly happens between terminal alkynes and organic azides. So far, only two examples of Cu(I) catalyzed cycloaddition of an internal alkyne and benzyl azide have been reported. The internal alkyne is coincidentally a symmetric alkyne, 3-hexyne. In this project, Cu(I)- catalyzed cycloaddition between internal gold(I) alkynyls and benzyl azides are going to be exploited. Shown in Scheme 1.5.2 is the strategy employed.

The synthesis of alkynylgold(I) has a long history. Akynylgold(I) complexes with various ligands are readily available from a simple reaction of gold(I) halides and terminal alkynes in the presence of a strong base. The gold(I) triazolates will then be

synthesized from internal gold(I) alkynyls with benzyl azide in the presence of a Cu(I) catalyst, in this particular case, [Cu(MeCN)4]PF6, under stirring at room temperature.

Scheme 1.5.2. Cu(I)-Catalyzed 1,3-Dipolar Cycloaddition of Gold(I) Alkynyls and Benzyl Azide.

New compounds, including new gold(I) alkynyls and triazolates will be fully characterized by NMR (31P{1H}, 1H and 13C{1H} when necessary), UV-vis and fluorescence spectroscopy, Mass spectrometry, elemental analysis and X-ray crystallography when applicable. The heavy atom effect of gold(I) will be discussed when polycyclic aromatic substituents with interesting optical properties are present.

C. Phosphine Au(I) Fragments as Electron Acceptors on Two-Photon Absorbing

Organic Skeletons.

Phosphine gold(I) fragments are isolobal with the proton, and considered as efficient electron acceptors. Meanwhile, the heavy atom effect of gold(I) fragments can potentially enhance the singlet oxygen generation efficiency when attached to a phosphorescent core. In this project, attachment of phosphine gold(I) fragments to two-photon absorbing centrosymmetric distyryl benzene and distyryl naphthalene

systems is going to be exploited. All these strong fluorescent organic skeletons will be assembled from commercially available starting materials using well-known organic synthetic methods, such as electrophilic bromination, Michaelis-Arbuzov reaction,

Horner-Wadsworth-Emmons reaction and Sonogashira coupling. Attachment of the gold(I) fragments involve the methods developed in the the first two projects. Direct

Au–C bond formation, attachment of a gold(I) alkynyl group and a triazolate group will all be studied. Both D–π–A–π–D systems with gold(I) fragments in the middle and A–π–D–π–A systems with gold(I) fragments in the end will be studied. Shown in

Figure 1.5.1 are the synthetic target compounds.

Figure 1.5.1. Synthetic Targets of Two-Photon Absorbing Gold(I) Complexes.

All the new compounds will be characterized by NMR (31P{1H} and 1H),

UV-vis and fluorescence spectroscopy, Mass spectrometry, elemental analysis and

X-ray crystallography when applicable. The two-photon absorption cross-sections and singlet oxygen generation efficiency of these compounds will be measured and compared.

D. Metalloazadipyrromethene Complexes for Solar Energy Conversion and Oxygen

Evolution

In the first part of this project, gold(I) and gold(III) azadipyrromethene

complexes will be synthesized. With the oxidation states of the gold centers two

electrons apart, these complexes support an oxidative addition/reductive elimination

sequence which can lead to the storage of solar energy in chemical bonds, Figure

1.5.2. By exciting the Au(III) azadipyrromethene complexes using UV light,

reductive elimination reaction occurs. The generated Au(I) center is capped by a

sacrificial ligand, such as an olefin, and Br2 will be captured by olefins to study the

photoelimination mechanism. Solid state photoelimination of Br2 will be carried out

and Br2 will be collected and stored as the solar energy carrier.

Figure 1.5.2. Storing Solar Energy in Chemical Bonds.

Shown in Scheme 1.5.3 is the strategy employed for the synthesis of Au(I) azadipyrromethene complexes. The two pyrrolic protons will first be substituted by

Br. After deprotonating the ligand with a strong base, the gold(I) halide starting material will be added and the reaction will be conducted at room temperature.

Scheme 1.5.3. Synthetic Strategy for Gold(I) Azadipyrromethene Complexes.

Gold(III) complexes will be synthesized either from the direct bromination of the gold(I) azadipyrromethene complexes, or by reacting Au(III) starting materials with azadipyrromethene ligands.

After the Au(III) and Au(I) azadipyrromethene complexes are successfully made and characterized, light-driven reductive elimination of Br2 from the Au(III) azadipyrromethene complexes will be conducted in solution with phosphines as the chemical trap. The same process will also be conducted in the solid state without the use of chemical trap. Br2 will be collected and stored as the solar energy carrier.

In photosynthesis, nature uses a polynuclear Ca-Mn4 heterocubane in photosystem II to oxidize water to oxygen. Manganese oxos are proposed to be involved in this oxidation.196 Bacterial heme enzymes, chlorite dismutases are also enzymes which can evolve oxygen. An iron oxo is proposed as the functional intermediate to manage the oxidation.197, 198 34

Scheme 1.5.4. Synthetic Strategy for Zinc, Vanadyl, Manganese, and Iron Complexes.

In the second part of this project, manganese and iron azadipyrromethene complexes will be synthesized as oxygen evolving models. Firstly, a tetradentate azadipyrromethene ligand, LOH will be synthesized following the literature procedures, Scheme 1.5.4. This ligand will then be reacted with Zn(OAc)2·H2O to demonstrate the structural and spectroscopic consequences upon metal binding because zinc is a spectroscopically silent ion that binds without ligand-field stabilization. A vanadyl complex will then be synthesized with VO(acetylacetonate)2, to predict whether LOH can support metal oxo complexes in tetragonal ligand fields.

Manganese and iron complexes will then be synthesized with Fe(OAc)2 and

Mn(OAc)2·H2O as the reduced form of oxygen-evolving compounds.

All these compounds will be characterized using X-ray crystallography. NMR spectra will not be collected due to solubility issues. Absorption and emission spectra will be collected to demonstrate the change in optical property upon metal binding.

The manganese and iron complexes will be further reacted with oxygen-atom donors to generate higher-valent metal oxos. These metal oxos will be reacted with H2O,

- - OH , or OCl to produce O2.

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Chapter 2. Synthesis and Characterization of Mono- and Di-Gold(I)

Naphthalene Complexes from Base-Promoted Auration

2.1. Introduction

Organogold compounds with at least one gold-to-carbon bond were among the first organometallic compounds to be discovered.1 The first organogold(I) complexes of the type R–Au–L (L, a two-electron donor ligand; R, an alkyl or an aryl group) were prepared in 1959.2 Coates and coworkers reported the first examples of alkylation/arylation of (phosphine)gold halides using organolithium reagents. Since then, numerous organogold(I) complexes have been synthesized.

Gold is known to be the most electronegative metal with a very small covalent and ionic radius.3 Quantum-chemical calculations combined with relativistic effects have demonstrated that the Au–C bonds are strongly directional following the sp/d hybridization model and have very low polarity.4 These unique properties make the organogold compounds among the most stable transition metal organometallics with discrete metal-to-carbon sigma-bonds. Usually, they are not affected by water and can only be cleaved by aggressive acids and bases.

Initial work in synthesizing organogold complexes primarily involved monogold compounds. It was not until late 1970s that polygold compounds were reported.5 Up to six gold(I) fragments could be attached to one carbon atom, with an octahedral

2+ 5 [(PPh3)Au]6C as the example. However, attaching gold(I) fragments to aromatic skeletons involves more research efforts.

The initial arylgold(I) chemistry only involved simple aromatics, such as phenyl and its polyfluoroaryl derivatives.6-8 Later research efforts extended the aromatic skeletons to vinylbenzene,9 biphenyl,3 and anthracene.10 The commonly used method was the metathesis between gold halides, LAuX and standard aryl transferring reagents such as Grignard reagents, organolithium, organothallium, and organomercury compounds (L = phosphines, isocyanides, arsine, carbenes; X =

Halides). Yip and coworkers successfully synthesized mono- and di-

11 PPh3Au(I)-pyrenyl complexes using n-butyllithium as the transferring reagent. A

12 similar method was also used to synthesize PPh3Au-2-naphthyl. Recently, synthesis of a dinuclear organogold(I) naphthalene complex from

1,8-bis(trimethylstannyl)naphthalene and [Au2Cl2(μ-Ph2P(CH2)2PPh2)] was reported.13 These reactions generally proceed fast, and can lead to decent isolated yields of the products. However, anhydrous and inert atmosphere are usually needed, and the rigid reaction conditions are not compatible with sensitive functional groups, such as nitro, aldehyde, ketone, and ester. Moreover, if not properly handled, the reduction of gold(I) starting materials into gold nanoparticles in the presence of these highly reductive organometallic reagents can easily happen, thus compromising the yields or resulting in no product isolated.

Inspired by the transmetalation process in palladium-catalyzed Suzuki-Miyaura

14, 15 - coupling and the observation of phenyl-group transfer from BPh4 to gold(I) in aqueous and non-aqueous media by the Schmidbaur and Fackler research groups,16, 17

Gray and coworkers developed a facile base-promoted auration process for

18 Au–Caromatic formation. In the presence of an inorganic salt, cesium carbonate, aryl groups transfer efficiently from boronic acids to aromatic skeletons in isopropyl alcohol. Pyrophoric reagents are completely avoided. Substrates with nitro, aldehyde and ester groups survive the reaction, and excellent yields were obtained. Moreover, this protocol is not limited to phenylboronic acid. Auration of ferrocenyl and thienyl boronic acid also proceeds efficiently.

Shown in Scheme 2.1.1 is an example of this base-promoted metalation in which naphthalene is aurated at the 1-position.

Cs2CO3 B(OH) + Cy3PAuBr AuPCy + BBr(OH)2 2 i-PrOH,  3 not isolated

Scheme 2.1.1. Base Promoted Auration of Napathalene at the 1-Position.

Naphthalene is one of the polycyclic aromatic systems which display intense

π→π* transitions in the UV and/or visible region. Shown in Figure 2.1.1 is a naphthalene molecule with its numbering system. If excited by UV light at room temperature, strong singlet-state emission which is not oxygen-quenchable can be observed. Figure 2.1.2 shows the combined absorption and emission spectra of free naphthalene in dichloromethane.

Figure 2.1.1. Naphthalene with its Numbering System.

6000 277 nm Napthalene 300 335 nm 268 nm 323 nm Solvent: CH Cl 5000 2 2 C=2E-5M -1 -1 250  (277 nm)= 5.4E3 M cm Ex: 277 nm

4000 (a.u.) Intensity Emission 287 nm 200 )

-1 3000 150 cm -1 (M  2000 100

1000 50

0 0 250 300 350 400 450 Wavelength (nm)

Figure 2.1.2. Absorption and emission of naphthalene in CH2Cl2.

By attaching a gold(I) fragment to the periphery of naphthalene, the heavy atom effect can potentially enhance the intersystem crossing from the fluorescing singlet state to its phosphorescing triplet state. Shown in Figure 2.1.3 are emission spectra of

PCy3Au-1-naphthyl collected in acetone. The highly structured emission is oxygen-quenchable, and also efficiently quenched by an oxidative quencher, methyl viologen (MV), which supports bimolecular electron transfer emission quenching.

These phenomena are consistent with the triplet-state nature of the emission.

60 Ex: 320 nm 0 M [PCy -Au-(1-naphthyl)] = 0.3 mM in acetone 3 2E-6 M Quencher: Methyl Viologen Hexafluorophosphate 4E-6 M 50 481 nm 6E-6 M 518 nm 8E-6 M 2E-5 M 40 4E-5 M 6E-5 M 2E-4 M 6E-4 M 30

557 nm 20

10 Emission Intensity (arbitrary unit) Intensity Emission 0 350 400 450 500 550 600

Wavelength (nm)

Figure 2.1.3. Emission Quenching of PCy3Au-1-Naphthyl by Methyl Viologen.

This interesting observation invites further study into gold(I) naphthalene complexes. 1-naphthalene-boronic acid and 2-naphthalene-boronic acid are 57 commercially available. Well-developed mild catalytic methods which install boronate esters onto aromatic molecules make the preparation of other naphthalene starting ligands possible. During the late 1990s, Miyaura and co-workers already disclosed the formation of arylpinacolboronate esters from bis(pinacolato)diboron and

19 20 aryl bromides, iodides, and triflates with (dppf)PdCl2 (dppf =

1,1-bis[diphenylphosphino]ferrocene) in the presence of potassium acetate in polar solvents. Shortly thereafter, Masuda and co-workers reported a similar boronation reaction using pinacolborane as the boron source and amines as supporting bases.21, 22

In 2001, Miyaura and collaborators reported reaction conditions that produce arylboronic esters from aryl chlorides and aryl bromides.23 In the following year,

Fürstner and Seidel used a microwave-assisted method to transform aryl chlorides into arylpinacolboronate esters.24 Recently, efficient palladium-catalyzed borylation reactions of aryl chlorides25 and aryl (pyrollyl) bromides26 were reported by

Buchwald and collaborators. These reactions require a supporting base and are promoted by dialkylbiarylphosphine ligands.

Much research effort has also been devoted to the direct borylation of arenes using transition-metal catalysts. In 2005, Marder and collaborators described iridium-catalyzed borylation reactions of naphthalene, pyrene, and perylene.27 These reactions bypass pre-functionalized reagents such as aryl iodides or triflates. They also differ in regioselectivity from electrophilic aromatic substitution. This regioselectivity possibly derives from an encumbered intermediate, the 16-electron species

[Ir(bpy)(Bpin)3] (bpy = 2,2-bipyridine; Bpin = pinacolboronato), which is proposed

58 to undergo a rate-limiting C–H bond activation step.28 Carbon-hydrogen bonds adjacent to ring junctures or substituents resist borylation. Napthalene-2-boronate and naphthalene-2,6-bis(boronate) were isolated in pure states.

Naphthalene-2,7-bis(boronate) was also synthesized, but was not isolated as pure product.29

Palladium- and iridium catalyzed borylation protocols are complimentary.

Palladium-catalyzed borylation requires halide or sulfonic ester reactants.

Iridium-based borylation is dominated by sterics and can produce functionalized aromatic molecules that classical methods achieve only with difficulty. However, they can produce mixtures of products that require nontrivial separation.

This chapter describes the synthesis and characterization of new mono- and di-gold naphthalenes from a base-promoted auration process. Naphthalene boronates will be synthesized using both the palladium-catalyzed cross-coupling reaction from naphthalene halides and the iridium-catalyzed borylation of free naphthalene. The formation of the products will be monitored using NMR spectroscopy and X-ray crystallography. The luminescence of the products will be measured and compared.

The heavy atom effect brought about by gold(I) attachment will be discussed.

Meanwhile, gold(I) starting materials with different ancillary ligands are going to be used to study their effect on the photophysical properties, solubility and stability of the final products. Control experiments will be done by reacting gold halides with naphthalene halides using n-butyllithium as the transferring agent.

2.2. Results and discussions

2.2.1. Synthesis and characterization of the borylated naphthalenes

Naphthalene-2-boronic acid (compound 4 in Scheme 2.2.1), which is commercially available, was directly used in the synthesis of monogold-naphthyl complexes. However, naphthalene molecules carrying two boronic acid groups are not commercially available. The reported iridium-catalyzed borylation of naphthalene developed by Marder’s group29 lead to the formation of naphthalene-2-boronate, naphthalene-2,6-boronate ester (C2h isomer), and naphthalene-2,7-boronate (C2v isomer). This method was followed here to synthesize naphthalene-2-boronate. A mixture of the C2h and the C2v isomer was collected. Isolation using column chromatography proved to be ineffective to separate the two isomers.

To synthesize the C2h and C2v isomer in their pure states, palladium(0)-catalyzed cross coupling of bis(pinacolato)diboron with the corresponding dibromonaphthalene was used, following a modified procedure developed by Miyaura and collaborators for the borylation of aryl chlorides and aryl bromides.23 The bis(dibenzylideneacetone)palladium(0)/tricyclohexylphosphine/potassium acetate

(Pd(dba)2/PCy3/KOAc) system proved to be effective in the synthesis. Pd(dba)2 and

PCy3 were first combined in degassed 1,4-dioxane, and stirred for 30 min. The mixture took on a dark red color. If the red color fades upon stirring, the catalyst system would lose its activity. To this catalyst system was added the starting material

(2,6-dibromonaphthalene or 2,7-dibromonaphthalene) and the base, and the reaction

60 mixture was stirred under argon at 80 °C overnight. The resulting reaction mixture usually took on a greenish color with a black suspension which is Pd(0) nanoparticles.

1,4-dioxane was removed under rotary evaporation, and the residue was dissolved in dichloromethane. The dichloromethane solution was then washed with water several times, and then dried with MgSO4. A yellowish solution was collected after filtration.

Upon removing the solvent, an oily yellow residue was obtained. Both isomers have melting points higher than 250 °C, and vacuum sublimation at 150-160 °C proved to be an efficient purification method.

Scheme 2.2.1 shows the detailed synthetic pathway for the three naphthalene boronate esters (compound 1, 2 and 3). The commercially available naphthalene-2-boronic acid was also used as an alternative, which is shown in

Scheme 2.2.1 as compound 4.

Scheme 2.2.1. Synthetic pathway for borylated naphthalenes.

The room temperature emission of dibromonapthalene starting materials shows the heavy atom effect of bromine. As seen in Figure 2.1.1, free naphthalene absorbs strongly in the UV region, with the absorption maximum at 277 nm. The singlet state emission (300-400 nm) was observed at room temperature. The emission spectrum was collected in air. This emission is not oxygen quenchable. With bromine attachment, the strong absorption in the UV region shifts to red, and an oxygen quenchable triplet-state emission band emerges at 490-600 nm. The singlet state emission is also observed. However, both the singlet and the triplet state emissions are very weak. Interestingly, even weaker emission spikes were observed around 700 nm, which might be due to further fine splitting of the excited triplet states. These spectra can be found in Appendix III.

The naphthalene boronic acid and boronate esters are all strong UV light absorbers. Their absorption experiences a clear red-shift compared to naphthalene.

The singlet state emission of the naphthalene is completely quenched in these molecules and a new structured triplet state emission appears around 700 nm. The emission peaks of the mono-substituted naphthalenes appear at lower wavelengths compared with the bis-substituted ones, as seen in Figure 2.2.1. These structured triplet state emissions are much stronger than that seen in dibromonaphthalenes, but experience a ~200 nm red shift.

600 700 Naphthalene-2-boronic acid in CH Cl 688 nm 280 nm 662 nm 2 2 2-bpin-naphthalene in CH Cl 5000 4000 2 2 600 280 nm 1.8 E-4 M 500 2.16E-4 M 690 nm Emission Intensity (a.u.) Ex: 318 nm Ex: 280 nm Emission Intensity (a.u.) 4000 500 400 3000 ) )

-1 400 -1 3000 300 cm cm -1 -1 2000 300 M (

(Ml 2000 

 200 723 nm 200 1000 1000 328 nm 327 nm 100 100

0 0 0 0 250 300 350 400 450 500 550 600 650 700 750 800 850 300 400 500 600 700 800 Wavelength (nm) Wavelength (nm)

250 5000 C 282 nm 2h C 8000 723 nm 2v 702 nm 200 2,6-dibpin-naphthalenein CH Cl 2,7-dibpin-naphthalene in CH Cl 2 2 200 4000 280 nm 2 2 Emission Intensity (a.u.)

1.05E-4 M 1.05 E-4 M Emission Intensity (a.u.) 694 nm 6000 293 nm Ex: 332 nm Ex: 332 nm 150 150 3000 ) ) -1 -1 737 nm cm 4000 cm 672 nm 100 -1 756 nm 100 -1 2000 (M (M  337 nm  332 nm 2000 50 1000 50

0 0 0 0 250 300 350 400 450 500 550 600 650 700 750 800 850 900 250 300 350 400 450 500 550 600 650 700 750 800 850 900 Wavelength (nm) Wavelength (nm)

Figure 2.2.1. Absorption and emission spectra for all the ligands.

2.2.2. Synthesis and Characterization of gold(I) naphthalene complexes

Scheme 2.2.2 shows the synthetic diagram of the targeted gold(I) naphthalene complexes. The reactions were carried out in 2-propanol, sometimes with benzene present to promote the dissolution of the starting materials. Cs2CO3, an inorganic base which is easy to remove from the product mixture, was used. Compared with other inorganic salt, such as lithium, sodium or potassium carbonate, cesium carbonate has higher solubility in organic solvents and easier to dissociate.30 All the reactions were carried out at 50 °C under argon protection. For more light sensitive compounds, covering the reaction vessel with aluminum foil during the reaction is necessary.

Scheme 2.2.2. Synthetic diagram for the gold(I) naphthalene complexes.

The chosen gold(I) starting materials involve three different ancillary ligands, tricyclohexylphosphine (PCy3), triphenylphosphine (PPh3) and a saturated

N-heterocyclic carbene (SIPr). Usually the gold bromide salts were used in the synthesis, but gold azide and gold acetate salts are also good starting materials.

Isolated yields are not affected upon switching the starting gold(I) materials. To synthesize the mono-gold complexes, the commercially available naphthalene-2-boronic acid and the synthesized naphthalene-2-boronic ester were both used. The ester is advantageous because it is soluble in hexanes while the products are not. The residual unreacted pinacolboronate ester can be washed away using hexanes without loss of yield. However, washing with methanol is necessary to remove the excess boronic acid. Because the products are partially soluble in methanol, the isolation yields are compromised. For all the reactions, the ligands were kept in excess. If the gold starting material is in excess, its surplus will contaminate the product and is difficult to remove. 64

The mono-gold complexes were isolated by benzene extraction. However, most of the digold complexes are not soluble in benzene, with the C2v-symmetric

PPh3-digold and SIPr-digold complexes being the exceptions. Extraction with dichloromethane proved to be effective for the isolation of the digold complexes. All the compounds were isolated in good to excellent yields, usually as white powders except compound 10, which is orange. Shown in Table 2.2.1 is the compiled synthetic information for all the targeted compounds. X-ray diffraction quality single crystals were grown for compound 5, 8 and 10 by diffusing pentane into a concentrated benzene solution, and crystals for 6, 7 and 9 were grown by layering ether onto a dichloromethane solution. Analytically pure samples for compound 11-13 were isolated from slow evaporation. Compared with compound 5 and 8, compound 11 is much more light-sensitive and unstable–the reaction mixture can quickly decompose upon addition of base even at ambient temperature.

Table 2.2.1. Gold(I) naphthalene complexes from base-promoted auration.

The progress of the reaction can be easily monitored by 31P{1H} NMR for the phosphine-ligated products, and 13C{1H} NMR for the NHC-ligated products. As seen in Table 2.2.2 and Table 2.2.3, compared to the starting materials, the 31P{1H} and the 13C{1H} peaks of the carbene carbon experience a clear downfield shift. The

31 1 P{ H} peaks for the PCy3Au-napththyl complexes resonate at about 58 ppm, and

13 1 those for PPh3Au-naphthalene complexes resonate at about 44 ppm. The C{ H} peaks for the carbene carbon of the SIPrAu-naphthalene complexes resonate at 220 ppm. These chemical shifts are very diagnostic of the Au-C bond formation in gold-aryl complexes.

Gold(I) 31P{1H} 31P{1H} solvent Starting Material Naphthalene Complexes (ppm)

PCy3AuBr (55.5)

PCy3Au-(2-naphthyl) C6D6 57.6 PCy3AuOAc (47.9)

PCy3AuN3 (53.9)

PPh3Au-(2-naphthyl) C6D6 44.0 PPh3AuBr (35.2)

2,6-(PCy3Au)2-naphthalene CDCl3 58.0 PCy3AuBr (55.5)

2,7-(PCy3Au)2- naphthalene CDCl3 58.0 PCy3AuBr (55.5)

2,6-(PPh3Au)2- naphthalene CDCl3 44.4 PPh3AuBr (35.2)

2,7-(PPh3Au)2- naphthalene CDCl3 44.4 PPh3AuBr (35.2)

31 1 Table 2.2.2. P{ H} chemical shifts relative to 85% H3PO4(aq) of phosphine-ligated gold complexes.

Gold(I) 13C{1H} 13C{1H} solvent Starting Material Naphthalene Complexes (carbene ppm)

SIPrAu-2- naphthalene C6D6 217.3 SIPrAuBr (199.0) SIPrAuBr (199.0) 2,6-(SIPrAu)2- naphthalene CDCl3 217.2 SIPrAuN3 (194.7)

2,7-(SIPrAu)2- naphthalene CDCl3 217.2 SIPrAuOAc (195.5)

Table 2.2.3. 13C{1H} chemical shifts of ligand carbene carbons relative to tetramethylsilane in NHC-ligated gold complexes.

The 1H NMR spectra were also collected to identify the purity of the products.

For the SIPr-Au complexes, the correct integration ratio of the protons assigned to the naphthalene ring to the ones assigned to the SIPr group also identifies the formation of the product. All the NMR spectra collected are shown in Appendix II.

Shown in Figure 2.2.2 are the thermal ellipsoid projections of three gold(I)-naphthalene complexes, including the monogold(I) complex, 5, and the C2h and C2v symmetric digold(I) complexes 9 and 10. The structures of 6, 7 and 8 can be found in Appendix I. Compound 8 is a known structure,12 prepared using n-butyllithium as the transfering reagent.

Figure 2.2.2 Crystal structures (100 K) of phosphine gold(I)-naphthalene complexes. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon.

The packing diagram of the structures reveals no short Au-Au distance suggestive of aurophilic interactions.

Table 2.2.4 collects the interatomic distances and angles. There is only one molecule in the asymmetric unit of 5 and 8. The asymmetric unit of 6 contains two half-molecules situated on special positions. In the asymmetric unit of 7, one complete molecule resides on a general position, and one half-molecule on a mirror plane. In the asymmetric unit of 9, one half-molecule resides on a crystallographic inversion center. Gold-carbon bond lengths range from 2.00(2) Å for one independent

C–Au bond of 7 to 2.051(4) Å for an independent bond in 10. Phosphorus-gold bonds range in length from 2.2643(16) Å for 9 to 2.2984(14) Å for 6. These ranges of gold(I)-element bond lengths are normal.31-33 Coordination geometries about gold are essentially linear: C–Au–P bond angles range from 172.04(10)° (one such angle in 10) to 179.08(15)° (one independent molecule of 6).

Compound 5 6 7 8 9 10

C–Au 2.038(3) 2.035(5) 2.026(19) 2.043(2) 2.023(5) 2.051(4) 2.044(5) 2.00(2) 2.036(3) 2.050(12) Au–P 2.2922(9) 2.2984(14) 2.303(4) 2.2941(6) 2.2643(16) 2.2874(9), 2.2968(14) 2.276(5) 2.2930(9) 2.291(3) C–Au–P 177.04(7) 178.75(16) 178.7(5) 178.12(7) 175.78(17) 172.04(10) 179.08(15) 176.0(6) 174.95(10) 177.4(5)

Table 2.2.4 Selected interatomic distances (Å) and angles (°) for aurated naphthalenes.

All the gold(I) naphthalene complexes luminesce at room temperature in organic solvents. Oxygen-quenchable, structured emission appears at wavelengths extending from ca. 475–650 nm. This emission onset represents a Stokes shift of about 145 nm

(9250 cm–1) from the onset of absorption. For complexes having the same number of gold atoms, peak emission wavelengths are somewhat insensitive to gold substitution about the naphthalene core. Figure 2.2.3 depicts room-temperature absorption and emission spectra of the new mono-gold 2-naphthyl complex 5 and of the isomeric di-gold substituted naphthalenes 6 and 7 recorded in dichloromethane. The naphthalene-centered absorptions occur near 330 nm. The absorption patterns differ according to the different substitution pattern of the naphthalene skeleton. A dual luminescence feature was observed for compound 5. The structured emission with a maximum at 334 nm exhibits an approximate mirror-image relationship with the absorption at 280 nm. The small Stokes shift (5700 cm–1) suggests that the fluorescence is from a singlet excited state. Comparatively, the singlet-state emission is much less prominent for compound 7, and it is almost completely quenched in compound 6.

For all gold(I) complexes, sharply structured emission appears near 470 nm. At least three vibronic peaks are clearly resolved with spacings that average 1425 cm–1 for 5, 1365 cm–1 for 6, and 1323 cm–1 for 7. These values concur roughly with tabulated ring-stretching frequencies of aromatic molecules, indicating a vibronic origin for the spiked structure of the 475–650 nm emission profile.34 The other gold(I) naphthalene complexes with PPh3 or SIPr ligands have similar absorption and

70 emission pattern. All of the lower energy emissions are oxygen-quenchable. These spectra can be found in Appendix III.

(a) 480 nm

20000 515 nm (a.u.) Intensity Emission

) 15000 –1 cm

–1

(M 10000 555 nm  280 nm 334 nm

5000 602 nm

0 300 400 500 600 700 Wavelength (nm)

(b) 50000

490 nm 40000 525 nm Emission Intensity (a.u.) Intensity Emission

) 30000 –1 cm

–1 20000 (M 565 nm  303 nm 314 nm 10000 613 nm 0 300 400 500 600 700 Wavelength (nm)

40000 (a.u.) Intensity Emission )

–1 30000

cm 563 nm

–1

(M 20000 

10000 345 nm 0 300 400 500 600 700 Wavelength (nm)

Figure 2.2.3. Absorption (black) and room-temperature emission (red) of (a) mono-gold 5, (b)

C2h-symmetric di-gold 6, and (c) C2v-symmetric di-gold 7 in CH2Cl2.

Compound Solvent T Emax(nm) λem  em kr × knr × (K) (nm)a (ms) 102 103 (s–1) (s–1) 5 2-MeTHF 295 479 480 0.097 0.0061 0.63 10.24 5 2-MeTHF 77 480 1.72 5 2-MeTHF 77 605 1.72 6 1:1 295 489 480 0.200 0.022 1.08 4.89

2-MeTHF/CH2Cl2 6 1:1 77 485 0.541

2-MeTHF/CH2Cl2 6 1:1 77 605 0.48

2-MeTHF/CH2Cl2 7 1:1 295 490 480 0.220 0.014 0.64 4.48

2-MeTHF/CH2Cl2 7 1:1 77 480 1.59

2-MeTHF/CH2Cl2 8 2-MeTHF 295 479 480 0.108 0.012 1.07 9.15 8 2-MeTHF 77 480 1.65 8 2-MeTHF 77 605 1.5 9 1:1 295 490 480 0.210 0.025 1.17 4.64

2-MeTHF/CH2Cl2 9 1:1 77 480 0.525

2-MeTHF/CH2Cl2 9 1:1 77 605 0.48

2-MeTHF/CH2Cl2 10 2-MeTHF 295 491 480 0.20 0.013 0.64 4.94 10 2-MeTHF 77 485 1.53 10 2-MeTHF 77 605 1.36 12 1:1 295 490 490 0.26 0.032 1.21 3.72

2-MeTHF/CH2Cl2 12 1:1 77 485 0.494

2-MeTHF/CH2Cl2 12 1:1 77 605 0.46

2-MeTHF/CH2Cl2 13 2-MeTHF 295 490 490 0.32 0.014 0.45 3.08 13 2-MeTHF 77 485 1.28 13 2-MeTHF 77 605 1.17

a Wavelength at which emission lifetime data were collected.

Table 2.2.5. Luminescence parameters of gold-substituted naphthalenes.

Table 2.2.5 summarizes the luminescence parameters of the gold(I) naphthalene complexes. All lifetimes of luminescence are microsecond-scale or longer at 77 and

295 K. The lifetimes of luminescence, along with the oxygen-quenchability of the emission and the large Stokes shifts, indicate triplet-state luminescence. The triplet state emission quantum yields were calculated using anthracene (ethanol solution) as the standard, and the detailed calculation is shown in Scheme 2.2.3. The

C2h-symmetric digold complex tends to have higher emission quantum yields, while their lifetimes of luminescence are the shortest. Changing the ancillary ligands has no obvious effect on the lifetimes of luminescence. The small range of emission maxima complicates standard energy-gap law analyses.35 Due to the purification difficulty, data for compound 11 was not collected.

2 A(STλ max)I s ηXxD ΦXST=Φ  A(xmaxxλ )I η ST D ST

A: Absorbance at Excitation Wavelength I: Intensity of Excitation Light : Refractive Index of Solvent D: Area Under Emission Spectra x: sample under measurement ST: emission standard  2 MeTHF 1.4055 

 CH22 Cl 1.4242  mix 1.4148  CH CH OH 1.36 32 Standard : Anthracene 0.27

Scheme 2.2.3. Triplet-state emission quantum yield calculation details.

2.3. Conclusions

In this chapter, nine gold(I) naphthalene compounds were synthesized using a base-promoted auartion method, including three monogold(I) complexes, three C2v symmetric and three C2h symmetric digold(I) complexes. These complexes were characterized using NMR, UV-vis, fluorescence spectroscopy, mass spectrometry, combustion elemental analysis and X-ray crystallography when diffraction quality crystals were available.

The synthetic protocol applies equally to phosphine or N-heterocyclic carbene co-ligands of gold. Pyrophoric reagents were entirely avoided and isolated yields range from 56% to 98%. Attempts to synthesize the digold complexes using dibromonaphthalenes and n-butyllithium yielded no product–either the phosphine gold(I) halide starting material or an orange residue indicating decomposition was isolated. All these compounds are soluble in dichloromethane and chloroform.

Monogold(I) complexes tend to have better solubility than the digold complexes with the same ancillary ligands. All the monogold compounds readily dissolve in benzene and THF, but most of the digold compounds do not. Compounds with SIPr ancillary ligands have the best solubility. The symmetry of the molecule also affects the solubility. The C2v isomers of digold complexes with PPh3 and SIPr ancillary ligands are soluble in benzene and THF, and the corresponding C2h isomers are not. The C2v isomer of the PPh3-substituted digold complex takes on an interesting orange color, with all the other complexes being white.

The Au-C formation was conveniently authenticated by 31P{1H} for the phosphine ligated complexes and 13C{1H} NMR for the carbene ligated complexes.

Compared with the starting materials, a downfield shift was observed for the phosphorus and the carbene carbon peaks. This kind of downfield shift is diagnostic of gold-carbon formation, with the aryl group being variable.

Collected X-ray crystal structures further authenticate the success of the synthesis. The geometry about gold is essentially linear. No short Au–Au distances were observed.

All these compounds have strong absorptions in the UV region, with the absorption maxima at ~300 nm. An oxygen-quenchable emission from 475-650 nm was observed at room temperature. Microsecond-scale or longer lifetimes of luminescence at 77 and 295 K were detected, which confirms the triplet-state nature of the luminescence. In some cases, singlet and triplet-state emissions coexist. The triplet-state emission bands are highly structured. The vibronic spacing characteristic of aromatic ring deformation modes indicate that the luminescence is centered on the polycyclic aromatic hydrocarbon core. This implies that the attachment of gold(I) to the periphery of the naphthalene molecule indeed promotes the spin-orbit coupling, populating the triplet excited states.

2.4. Experimental

2.4.1. Reagents

Commercially available reagents were used as received without further purification, unless otherwise specified. The gold(I) starting materials, Au(tht)Cl,

PCy3AuCl, PCy3AuBr, PPh3AuCl, PPh3AuBr, PPh3AuOAc, SIPrAuCl, SIPrAuBr,

SIPrAuOAc were synthesized based on the literature procedures.36-39

2.4.2. Instrumentation

NMR Spectroscopy. NMR spectra (1H, 13C{1H}, and 31P{1H}) were recorded on a Varian AS-400 spectrometer. Chemical shifts are reported in parts-per-million

1 13 1 31 1 relative to Si(CH3)4 ( H, C{ H}), or 85% aqueous H3PO4 ( P{ H}).

Elemental Analysis and Mass Spectrometry. Microanalyses (C, H, and N) were performed by Robertson Microlit Laboratories. Mass spectrometry was performed at the University of Cincinnati Mass Spectrometry facility.

Optical Property Characterizations. UV-vis spectra were collected on a Cary

500 spectrophotometer in degassed HPLC grade solvents. Fluorescence measurements were done with a Cary Eclipse Spectrophotometer at room temperature.

All samples were purged with argon for at least 15 min prior to acquisition of the luminescence measurement. Steady state emission spectra were recorded at room temperature on an automated Photon Technology International (PTI) QM 4 fluorimeter equipped with a 150-W Xe arc lamp and a Hamamatsu R928 photomultiplier tube. Excitation light was excluded with appropriate glass filters.

Sample solutions were added to a quartz EPR tube, freeze pump thaw degassed (4 cycles, 1 × 10–5 Torr) and flame sealed. Low temperature emission spectra were recorded in rigid solvent glass at 77 K by immersion of the sealed EPR tubes into a liquid nitrogen-filled dewar.

X-Ray Structure Determinations. Single crystal X-ray data were collected on a

Bruker AXS SMART APEX CCD diffractometer using monochromatic Mo K radiation with the omega scan technique. The unit cells were determined using

SMART and SAINT+. Data collection for all crystals was conducted at 100 K

(-173.5C). All structures were solved by direct methods and refined by full matrix least squares against F2 with all reflections using SHELXTL. Refinement of extinction coefficients was found to be insignificant. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in standard calculated positions and all hydrogen atoms were refined with an isotropic displacement parameter 1.2 times that of the adjacent carbon. Compound 6 crystallized with one molecule of methylene chloride disordered over three sites with occupancy rates of

0.526(3), 0.301(6), and 0.173(6). Its C-Cl distances were restrained to be the same, and the ADPs of the disordered dichloromethane atoms were restrained to be similar

(SIMU and DELU commands in SHELXTL). Atoms C16 and C48, which overlap significantly, were restrained to be isotropic within a standard deviation of 0.02 Å2

2.4.3. Synthesis of the Ligands and Gold-Naphthalene Complexes

(4,4,5,5-tetramethyl-2-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen

-6-yl)-1,3,2-dioxaborolane) (2) and

4,4,5,5-tetramethyl-2-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-

7-yl)-1,3,2-dioxaborolane (3)

2,7-dibromonaphthalene or 2,6-dibromonaphthalene (0.1222 g, 0.40 mmol),

Bis(pinacolato)-diboron (0.2064 g, 0.81 mmol), and potassium acetate (KOAc)

(0.1264 g, 1.3 mmol) were combined in 5 mL 1,4-dioxane, and degassed (solution 1).

Bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) (14 mg, 6 mol%), and tricyclohexylphosphine (PCy3) (16.3 mg, 2.4 equv. of Pd(dba)2) were combined in 5 mL degassed 1,4-dioxane, and the resultant red solution was stirred for 30 min

(solution 2). Solution 1 was added to solution 2 with a pipette under stirring. After stirring for 10 min, the mixture was immersed in an 80 °C oil bath, and stirred under

Ar. Upon heating and stirring, the reaction mixture turned slightly yellow, which evolved into a black suspension. After 24 h, 1,4-dixoxane was removed by rotary evaporation. The product was extracted into 100 mL dichloromethane. The yellow dichloromethane solution was then washed with water twice, and the organic layer was collected and dried over MgSO4. The solution was filtered through a layer of silica gel and celite under vacuum. The solvent was removed and a yellow solid was collected. Sublimation under vacuum at 150–160 °C yielded the analytically pure white product.

1 Yield for 2: 51%. H NMR (CDCl3): δ (ppm) 8.41(s, 2H, naphthalene), 7.83(dd, 4 H,

1 J = 5.2 Hz, 8 Hz, naphthalene), 1.383 (s, 24 H, C(CH3)4). Yield for 3: 55%. H NMR

(CDCl3): δ (ppm), 8.35 (s, 2H, naphthalene), 7.83(dd, 4 H, J = 6 Hz, 8 Hz, naphthalene), 1.387 (s, 24 H, C(CH3)4)

These two materials were only analyzed by NMR, and the NMR pure materials were used for the synthesis of gold complexes.

(PCy3)Au-(2-naphthyl) (5): [(PCy3Au)Br] (88 mg, 0.16 mmol), 2-Bpin-naphthalene

(78.8 mg, 0.31 mmol), Cs2CO3 (197 mg, 0.60 mmol) were suspended in 12 mL isopropyl alcohol and added to a round bottom flask. After degassing, the reaction vessel was immersed in a 50 °C oil bath, and stirred under Ar for 24 h. After cooling, isopropyl alcohol was removed under rotary evaporation, and the remaining solid was extracted into 50 mL of benzene and filtered through celite. Benzene was then removed by rotary evaporation. The residue was washed using hexanes twice and triturated with pentane. After removing pentane under rotary evaporation, a white solid was collected. The white solid was then dissolved in a minimum amount of benzene and filtered through celite. Recrystallization by diffusing pentane into the concentrated benzene solution afforded the product as colorless crystals. Yield: 61.6

1 mg, 63.7%. H NMR(C6D6): δ (ppm) 8.58 (d, 1H, J = 6 Hz, 2-naphthyl), 8.28 (dd, 1H,

J = 8 Hz, 4.4 Hz, 2-napththyl), 7.92 (d, 1H, J = 8 Hz, 2-naphthyl), 7.86 (d, 1H, J = 8

Hz, 2-naphthyl); 7.78 (d, 1H, J = 8 Hz, 2-naphthyl), 7.24-7.36 (m, 2H, 2-naphthyl),

31 1 + 1.39-1.90 (m, 33H, C6H11). P{ H} NMR (C6D6): δ (ppm) 57.6. HR-MS (ES ): Calcd.

+ m/z = 605.2612 (M+H) , Found m/z = 605.2571. Anal. Calcd. for C28H40AuP: C,

55.63; H, 6.67. Found: C, 55.65; H, 6.82. UV-vis (THF):  () 279 nm (5.9 × 103

M-1cm-1), 289 nm (5.7 × 103 M-1cm-1), 300 nm (3.8 × 103 M-1 cm-1), 325 nm (256 M-1 cm-1). Emission (THF, ex. 279 nm): 355 nm, 480 nm, 516 nm, 553 nm, 600 nm. A

56% yield was obtained when using [(PCy3Au)N3] as the starting material in an otherwise analogous procedure.

2,6-Bis[(PCy3)Au]naphthalene (6): [(PCy3Au)Br] (176 mg, 0.32 mmol),

2,6-(Bpin)2-naphthalene (66.9 mg, 0.176 mmol), Cs2CO3 (230 mg, 0.704 mmol) were suspended in 5 mL isopropyl alcohol and charged into a round bottom flask. Benzene

(5 mL) was then added to promote dissolution of the starting materials. After degassing, the reaction vessel was immersed in a 50 °C oil bath, and stirred under Ar for 24 h. After cooling, the solvents were removed under rotary evaporation, and the remaining solid was extracted into 100 mL of dichloromethane. The extract was filtered through celite. Dichloromethane was removed by rotary evaporation. The residue was washed using hexanes twice and triturated with pentane. After removing pentane under vacuum filtration, an off-white solid was collected. The solid was washed with water and hexanes, and dried under vacuum. The solid was then dissolved in a minimum amount of dichloromethane and filtered through celite.

Layering ether onto this dichloromethane solution yielded 6 as colorless crystals.

1 Yield: 156 mg, 90%. H NMR (CDCl3): δ (ppm) 7.85 (d, 2H, J = 5.6 Hz, naphthalene),

7.63-7.64 (m, 2H, naphthalene), 7.55-7.58 (m, 2H, naphthalene) 1.55-2.10 (m, 66H,

31 1 + (C6H11)2). P{ H} NMR (CDCl3): δ (ppm) 57.965. HR-MS (ES ): Calcd. m/z =

+ 1081.4519 (M+H) ; Found m/z = 1081.4612. Anal. Calcd. for C46H72Au2P2: C, 51.11;

4 -1 H, 6.71. Found: C, 50.84; H, 6.62. UV-vis (CH2Cl2):  () 260 nm (5.74 × 10 M cm-1), 294 nm (1.30× 104 M-1 cm-1), 304 nm (1.6 × 104 M-1 cm-1), 314 nm (1.3 × 104

-1 -1 4 -1 -1 M cm ), 333 nm (1.18 × 10 M cm ). Emission (CH2Cl2, ex. 314 nm): 404 nm,

490 nm, 525 nm, 565 nm, 610 nm.

2,7-Bis[(PCy3)Au]naphthalene (7): [(PCy3Au)Br] (176 mg, 0.32 mmol),

2,7-(Bpin)2-naphthalene (73 mg, 0.192 mmol), Cs2CO3 (250 mg, 0.768 mmol) were suspended in 5 mL isopropyl alcohol and charged into a round bottom flask. Benzene

(5 mL) was added to promote dissolution. After degassing, the reaction vessel was immersed in a 50 °C oil bath, and stirred under Ar for 24 h. Solvents were removed under rotary evaporation, and the remaining solid was extracted into 100 mL of dichloromethane; the extract was filtered through celite. Dichloromethane was removed under rotary evaporation. The residue was washed using hexanes, and water several times and was triturated with pentane. After removing pentane under rotary evaporation, an off-white solid was collected. The solid was then dissolved in a minimum amount of dichloromethane and filtered through celite. Layering ether onto this dichloromethane solution yielded 7 as colorless crystals. Yield: 147 mg, 85%.

31 1 1 P{ H} NMR (CDCl3): δ (ppm) 57.956. H NMR (CDCl3): δ (ppm) 7.87 (d, 2H, J =

5.2 Hz, naphthalene), 7.59-7.62 (m, 2H, naphthalene), 7.50-7.52 (m, 2H, naphthalene)

1.56-2.10 (m, 66H, (C6H11)2). Anal. Calcd. for C46H72Au2P2: C, 51.11; H, 6.71. Found:

4 -1 -1 C, 50.98; H, 6.64. UV-vis (CH2Cl2)  () 260 nm (6.98×10 M cm ). Emission

(CH2Cl2, ex. 307 nm): 373 nm, 490 nm, 524 nm, 560 nm.

(PPh3)Au-(2-naphthyl) (8): [(PPh3Au)Br] (172 mg, 0.32 mmol), naphthalene-2-boronic acid (110 mg, 0.64 mmol), Cs2CO3 (196 mg, 0.60 mmol) were suspended in 10 mL isopropyl alcohol and charged into a round bottom flask. After degassing, the reaction vessel was immersed in a 50 °C oil bath, and stirred under Ar for 24 h. Isopropyl alcohol was removed under rotary evaporation, and the remaining solid was extracted into 50 mL benzene and filtered through celite. Benzene was removed under rotary evaporation. The residue was triturated with pentane and the resulting powder was transferred to a vacuum filtration frit, washed with methanol, water and pentane, and a white solid was collected. The white solid was then dissolved in a minimum amount of benzene and filtered through celite.

Recrystallization by diffusing pentane into the concentrated benzene solution afforded

1 the product as slight yellow crystals. Yield: 107 mg, 56.9%. H NMR (C6D6): δ (ppm)

8.57 (d, 1H, J = 6 Hz 2-naphthyl), 8.28 (dd, 1H, J = 8 Hz, 4.8 Hz, 2-naphthyl), 7.93 (d,

1H, J = 8 Hz, 2-naphthyl), 7.87 (d, 1H, J = 8 Hz, 2-naphthyl), 7.79 (d, 1H, J = 7.6 Hz,

2-naphthyl), 7.42-7.48 (m, 5H, tri-phenyl), 7.26-7.40 (m, 2H, 2-naphthyl), 6.90-7.00

31 1 + (m, 10H, tri-phenyl). P{ H} NMR (C6D6): δ (ppm) 44.0. HR-MS (ES ): Calcd. m/z

+ = 587.1198 (M+H) ; Found m/z = 587.1138. Anal. Calcd. for C28H22AuP: C, 57.35;

H, 3.78. Found: C, 57.23; H, 3.65. UV-vis (THF):  () 276 nm (8.7 × 103 M-1 cm-1),

290 nm (7.6×103 M-1 cm-1), 300 nm (5.4×104 M-1 cm-1), 325 nm (378 M-1 cm-1).

Emission (THF, ex. 275 nm): 353 nm, 481 nm, 516 nm, 555 nm, 600 nm.

2,6-Bis[(PPh3)Au]naphthalene (9): [(PCy3Au)Br] (168.7 mg, 0.31 mmol) and a mixture of 2,6-(Bpin)2-naphthalene (65.6 mg, 0.173 mmol), Cs2CO3 (224 mg, 0.69 mmol) were suspended in 20 mL isopropyl alcohol and charged into a round bottom flask. Benzene (10 mL) was added to promote solubility. After degassing, the reaction vessel was immersed in a 40 °C oil bath, and stirred under Ar for 24 h. Isopropyl alcohol was removed under rotary evaporation, and the remaining solid was extracted into 100 mL of dichloromethane and filtered through celite. Dichloromethane was removed under rotary evaporation. The residue was triturated with pentane, and vacuum filtered. After triturating with hexanes twice, a slightly yellow solid was collected. The solid was then dissolved in a minimum amount of dichloromethane and filtered through celite. Recrystallization by layering ether onto this dichloromethane solution afforded the product as colorless crystals. Yield: 169.7 mg, 92.5%. 1H

NMR(CDCl3): δ (ppm) 7.97 (d, 2H, J = 5.6 Hz, naphthalene), 7.61-7.69 (m, 16H,

31 1 aromatic H), 7.44-7.52 (m, 18H, aromatic H). P{ H} NMR (CDCl3): δ (ppm) 44.39.

HR-MS (ES+): Calcd. m/z = 1045.1697 (M+H)+; Found m/z = 1045.1682. Anal.

Calcd. for C46H36Au2P2: C, 52.89; H, 3.47. Found: C, 52.53; H, 3.40. UV-vis

4 -1 -1 4 -1 -1 (CH2Cl2):  () 261 nm (8.74 × 10 M cm ), 296 nm (2.07 × 10 M cm ), 308

4 -1 -1 4 -1 -1 nm(2.88 × 10 M cm ), 320 nm (2.47 × 10 M cm ). Emission (CH2Cl2, ex. 326 nm): 344 nm, 490 nm, 524 nm, 565 nm, 614 nm.

2,7-Bis[(PPh3)Au]naphthalene (10): The same procedure was used as for 9.

Sparkling grayish plates were obtained as the products. Recrystallization by diffusing ether into the concentrated benzene solution afforded amber crystals. Yield: 98%. 1H

NMR (CDCl3, 400): δ (ppm) 7.98 (d, 2H, J = 6 Hz, naphthalene), 7.58-7.69 (m, 16H,

31 1 aromatic H), 7.44-7.53 (m,18H, aromatic H). P { H} NMR (CDCl3): δ (ppm) 44.38.

Anal. Calcd. for C46H36Au2P2: C, 52.89; H, 3.47. Found: C, 52.87; H, 3.29. UV-vis

3 -1 -1 (CH2Cl2):  () 290 nm (2.7 × 10 M cm ). Emission (CH2Cl2, ex. 310 nm): 345 nm,

361 nm, 380 nm, 490 nm, 525 nm, 563 nm, 680 nm, 724 nm, 760 nm.

(SIPr)Au-(2-naphthyl) (11): [(SIPr)AuBr] (214 mg, 0.32 mmol) and naphthalene-2-boronic acid (55 mg, 0.32 mmol), were suspended in 20 mL isopropyl alcohol and charged into a round bottom flask. Benzene (10 mL) was then added to the flask to promote dissolution. After degassing, the reaction vessel was immersed in a 45 °C oil bath, and stirred under Ar overnight. Cs2CO3 (208 mg, 0.64 mmol) was then transferred into the flask quickly under Ar, and the reaction mixture was kept stirring in the oil bath for another 36 h. The reaction flask was cooled down and the solvents were removed under rotary evaporation. Approximately 20 mL of benzene was used to extract the products from the remaining residue. The benzene solution was filtered through celite, and a light yellow solution was collected. Benzene was removed under rotary evaporation. The residue was triturated with pentane and an off-white solid was collected. This solid was then dissolved in a minimum amount of benzene, and hexanes were layered onto the solution. Slow evaporation gives a

84 precipitation which was the analytically pure product. Yield: 156.2 mg, 68%. 1H

NMR (C6D6): δ (ppm) 7.88 (s, 1H, 2-naphthyl), 7.59 (s, 2H, 2-naphthyl), 7.55 (q, 2H,

J = 8 Hz, 2-naphthyl), 7.22 (t, 2H, J = 8 Hz, CH aromatic), 7.12 (q, 1H, J = 1.6 Hz,

2-naphthyl), 7.10 (s, 2H, CH aromatic), 7.08 (s, 2H, 2-naphthyl) 3.19 (s, 4H, CH2 imidazole), 3.09 (septet, 4H, J = 6.8 Hz, CH(CH3)2), 1.60 (d, 12H, J = 6.8 Hz,

13 CH(CH3)2), 1.21 (d, 12H, J = 6.8 Hz, CH(CH3)2). C NMR (C6D6): δ (ppm) 217.3 (s,

C carbene), 168.3 (s, naphthyl), 146.9 (s, CH aromatic), 139.9 (s, naphthyl), 139.5 (s, naphthyl), 135.2 (s, naphthyl), 134.3 (s, CH aromatic), 132.9 (s, naphthyl), 129.9 (s,

CH aromatic), 125.2 (s, naphthyl), 124.5 (s, CH aromatic), 124.2 (s, naphthyl), 123.5

(s, naphthyl), 53.5 (s, CH2 imidazole), 29.2 (s, CH(CH3)2), 25.4 (s, CH(CH3)2), 24.1 (s,

+ + CH(CH3)2). HR-MS (ES ): Calcd. m/z = 715.3326 (M+H) ; Found m/z = 715.3331.

Anal. Calcd. for C37H45AuN2: C, 62.21; H, 6.35; N, 3.92. Found: C, 61.95; H, 6.38; N,

3.81. UV-vis (THF):  () 326 nm (245.57 M-1 cm-1). Emission (THF): 360 nm, 371 nm, 480 nm, 516 nm, 556 nm, 598 nm.

2,6-Bis[(SIPr)Au]naphthalene (12): [(SIPrAu)Br] (214 mg, 0.32 mmol),

2,6-(Bpin)2-naphthalene (67.3 mg, 0.176 mmol), Cs2CO3 (230 mg, 0.704 mmol) were suspended in 20 mL isopropyl alcohol and charged into a round bottom flask. After degassing, the reaction vessel was immersed in a 45 °C oil bath, and stirred under Ar for 24 h. Isopropyl alcohol was removed under rotary evaporation, and the remaining solid was extracted into 100 mL of dichloromethane and filtered through celite.

Dichloromethane was removed under rotary evaporation. The residue was washed

85 using hexanes twice and was then triturated with pentane. After removing pentane under rotary evaporation, an off-white solid was collected. This solid was then dissolved in a minimum amount of dichloromethane, and hexanes were layered onto the solution. Slow evaporation gave a precipitate that was the analytically pure

1 product. Yield: 189 mg, 91%. H NMR (CDCl3) δ (ppm): 7.34 (t, 4H, J = 8 Hz, CH aromatic), 7.18 (d, 8H, J = 8 Hz), 7.08-7.11 (m, 4H, naphthalene), 6.89 (d, 2H, J = 8

Hz, naphthalene), 3.97 (s, 8H, CH2 imidazole), 3.13 (septet, 8H, J = 6.8 Hz,

CH(CH3)2), 1.44 (d, 24 H, J = 7.2 Hz, CH(CH3)2), 1.32 (d, 24H, J = 7.2 Hz,

13 CH(CH3)2). C NMR (CDCl3) δ (ppm): 217.2 (s, C carbene), 164.0 (s, naphthalene),

146.7 (s, CH aromatic), 138.2 (s, naphthalene), 137.4 (s, naphthalene), 134.8 (s, CH aromatic), 132.1 (s, naphthalene), 129.3 (s, naphthalene), 124.2 (s, CH aromatic),

123.9 (s, naphthalene), 53.7 (s, CH2 imidazole), 29.0 (s, CH(CH3)2), 25.1 (s,

+ + CH(CH3)2), 24.1 (s, CH(CH3)2)). HR-MS (ES ): Calcd. m/z = 1303.6100 (M+2H) ;

Found m/z =1301.6012 (M+), 1302.6067 (M+H)+, 1303.6012 (M+2H)+. Anal. Calcd. for C64H82Au2N4: C, 59.05; H, 6.35; N, 4.30. Found: C, 58.90; H, 5.96; N, 3.99.

4 -1 -1 UV-vis (CH2Cl2):  () 310 nm (1.39 × 10 M cm ). Emission (CH2Cl2, ex. 324 nm):

490 nm, 524 nm, 564 nm, 611 nm.

2,7-Bis[(SIPr)Au]naphthalene (13): [(SIPrAu)OAc] (103.5 mg, 0.16 mmol),

2,6-(Bpin)2-naphthalene (36.7 mg, 0.096 mmol), Cs2CO3 (127 mg, 0.40 mmol) were suspended in 5 mL isopropyl alcohol and charged into a round bottom flask. Benzene

(5 mL) was added to promote solubility. After degassing, the reaction vessel was

86 immersed in a 45 °C oil bath, and stirred under Ar for 48 h. Isopropyl alcohol was then removed under rotary evaporation, and the remaining solid was extracted into 50 mL of benzene and filtered through celite. Benzene was then removed under rotary evaporation. The residue was washed using hexanes twice and triturated with pentane.

After removing pentane under rotary evaporation, an off-white solid was collected.

Vapor diffusion of ether into concentrated benzene solution yielded no crystals.

Evaporative concentration produced an amber solid that was the analytically pure

1 product. Yield: 66 mg, 63%. H NMR (CDCl3): δ (ppm) 7.38 (t, 4H, J = 5.6 Hz, CH aromatic), 7.23 (d, 8H, J = 5.6 Hz, naphthalene), 7.15 (d, 2H, J = 8 Hz, naphthalene),

7.09 (s, 2H, naphthalene), 6.83 (d, 2H, J = 8 Hz, naphthalene) 3.99 (s, 8H, CH2 imidazole), 3.16 (septet, 8H, J = 6.8 Hz, CH(CH3)2), 1.48 (d, 24 H, J = 7.2 Hz,

13 CH(CH3)2), 1.35 (d, 24H, J = 7.2 Hz, CH(CH3)2). C NMR (CDCl3): δ (ppm) 217.2 (s,

C carbene), 164.9 (s, naphthalene), 146.7 (s, CH aromatic), 138.0 (s, naphthalene),

136.7 (s, naphthalene), 134.8 (s, CH aromatic), 133.4 (s, naphthalene), 130.4 (s, naphthalene), 129.3 (s, naphthalene), 124.2 (s, CH aromatic), 123.9 (s, naphthalene),

53.7 (s, CH2 imidazole), 28.9 (s, CH(CH3)2), 25.1 (s, CH(CH3)2), 24.0 (s, CH(CH3)2)).

Anal. Calcd. for C64H82Au2N4: C, 59.05; H, 6.35; N, 4.30. Found: C, 59.33; H, 6.52;

4 -1 -1 N, 4.22. UV-vis (CH2Cl2):  () 313 nm (6.4×10 M cm ). Emission (CH2Cl2, ex.

313 nm): 355 nm, 370 nm, 490 nm, 526 nm, 564 nm, 609 nm.

2.5. References

1. Schmidbaur, H. Chem. Soc. Rev. 1995, 391-400.

2. Calvin, G.; Coates, G. E.; Dixon, P. S. Chem. Ind. 1959, 1628.

3. Porter, K. A.; Schier, A.; Schmidbaur, H. Perspectives in Organometallic

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Chem. Soc. 1984, 106, 3387-3396.

5. Schmidbaur, H. Gold Bull. 1990, 23, 11-21.

6. Usón, R.; Laguna, A. Coor. Chem. Rev. 1986, 70, 1-50.

7. Schmidbaur, H. Gold Progress in Chemistry Biochemistry and Technology;

Wiley: Chichester, U. K. p648, 1999.

8. Bardají , M.; Jones, P. G.; Laguna, A.; Moracho, A.; Fischer, A. K. J.

Org.Chem. 2002, 648, 1-7.

9. Croix, C.; Balland-Longeau, A.; Allouchi, H.; Giorgi, M.; Duchene, A.;

Thibonnet, J. J. Organomet. Chem. 2005, 690, 4835-4843.

10. Yam, V. W. W.; Cheung, K. L.; Yip, S. K.; Zhu, N. Y. Photochem. Photobiol.

Sci. 2005, 4, 149-153.

11. Heng, W. Y.; Hu, J.; Yip, J. H. K. Organometallics 2007, 26, 6760-6768.

12. Osawa, M.; Hoshino, M.; Hashizume, D. Dalton Trans. 2008, 2248-2252.

13. Meyer, N.; Lehmann, C. W.; Lee, T. K. M.; Rust, J.; Yam, V. W. W.; Mohr, F.

Organometallics 2009, 28, 2931-2934.

14. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.

15. Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41, 4176-4211.

16. Sladek, A.; Hofreiter, S.; Paul, M.; Schmidbaur, H. J. Organometallic Chem.

1995, 501, 47-51.

17. Forward, J. M.; Fackler, J. P.; Staples, R. J. Organometallics 1995, 14,

4194-4198.

18. Partyka, D. V.; Zeller, M.; Hunter, A. D.; Gray, T. G. Angew. Chem., Int. Ed.

2006, 45, 8188-8191.

19. Ishiyama, T.; Murata, M.; Miyaura, N. J. Org.Chem. 1995, 60, 7508-7510.

20. Ishiyama, T.; Itoh, Y.; Kitano, T.; Miyaura, N. Tetrahedron Lett. 1997, 38,

3447-3450.

21. Murata, M.; Watanabe, S.; Masuda, Y. J. Org. Chem. 1997, 62, 6458-6459.

22. Murata, M.; Oyama, T.; Watanabe, S.; Masuda, Y. J. Org.Chem. 2000, 65,

164-168.

23. Ishiyama, T.; Ishida, K.; Miyaura, N. Tetrahedron 2001, 57, 9813-9816.

24. Fürstner, A.; Seidel, G. Org. Lett. 2002, 4, 541-543.

25. Billingsley, K. L.; Barder, T. E.; Buchwald, S. L. Angew. Chem. Int. Ed. 2007,

46, 5359-5363.

26. Billingsley, K. L.; Anderson, K. W.; Buchwald, S. L. Angew. Chem., Int. Ed.

2006, 45, 3484-3488.

27. Coventry, D. N.; Batsanov, A. S.; Goeta, A. E.; Howard, J. A. K.; Marder, T. B.;

Perutz, R. N. Chem. Commun. 2005, 2172-2174.

28. Tamura, H.; Yamazaki, H.; Sato, H.; Sakaki, S. J. Am. Chem. Soc. 2003,

16114-16126.

29. Coventry, D. N.; Batsanov, A. S.; Goeta, A. E.; Howard, J. A. K.; Marder, T. B.;

Perutz, R. N. Chem. Commun. 2005, 2172-2174.

30. Flessner, T.; Doye, S. J. Prak. Chem-Chem. ZTG. 1999, 341, 186-190.

31. Partyka, D. V.; Updegraff, J. B.; Zeller, M.; Hunter, A. D.; Gray, T. G.

Organometallics 2007, 26, 183-186.

32. Porter, K. A.; Schier, A.; Schmidbaur, H. Organometallics 2003, 22,

4922-4927.

33. Fernández, E. J.; Laguna, A.; Olmos, M. E. Coor. Chem. Rev. 2008, 252,

1630-1667.

34. Pretsch, E.; Buhlmann, P.; Affolter, C. Structure Determination of Organic

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Organometallics 1991, 10, 2178-2183.

Chapter 3. Copper-Catalyzed Huisgen [3+2] Cycloaddition of Gold(I)

Alkynyls with Benzyl Azide

3.1. Introduction

When explaining the mechanism of Cu(I)-catalyzed azide-alkyne cycloaddition

(CuAAC), the most popular and simplified idea is that the catalyst first forms a π complex with a terminal alkyne (LCu≡R). This copper alkynyl complex further reacts with an organic azide to form a copper triazolate intermediate, which undergoes proteolysis to release a triazole.1 However, both the copper alkynyl and the copper triazolate intermediates are hard to be isolated, and their identities are still under intensive research study.2

Comparatively, gold(I) alkynyls of the type LAuC≡CR are among the oldest organometallics,3, 4 with L being an organophosphine ligand, an N-heterocyclic carbene (NHC) ligand, or even the ammonia molecule.5 They are most commonly prepared in reactions of gold(I) halides with deprotonated alkynyl anions6, 7 and by ligand disruption of polymeric gold(I) acetylides,8-11 or by proton interchange of gold acetylacetonate complexes with terminal alkynes.12, 13 The resulting compounds are stable in air, and some are water-stable and even water-soluble.14 The two-coordinate, linear binding geometry about gold together with the linearity of the carbon-carbon triple bond imparts a rigid-rod topology of the (alkynyl)gold(I) moiety. This allows gold(I) alkynyls to find use as supramolecular synthons,15-18 notably in the preparation of catenanes.19, 20 Multinuclear gold(I) complexes, including dendrimers, can be

91 synthesized by reacting organic precursors bearing several terminal alkyne functionalities with gold(I) starting materials. The rod-like character of (alkynyl)gold complexes has also promoted investigation of liquid-crystalline behavior.21, 22 Current research in (alkynyl)gold(I) species predominately concerns their luminescence properties. Their emission is either from the inter- or intramolecular interactions between gold(I) centers,23-25 or from the triplet excited-state manifold of the alkynyl ligand itself promoted by the heavy atom effect of gold.26 Some compounds have luminescence responding to remote perturbation. For example, gold(I) alkynyls bearing pendant crown ether- or calixarene moieties27-30 are cation sensors, some with selectivity for potassium over sodium in dichloromethane/methanol mixtures.30

The chemical reactivity of the gold-bound carbon-carbon triple bond has been relatively under-explored. In 2007, Gray’s research group reported the synthesis of gold(I) triazole complexes by reacting phosphinegold(I) alkynyls with a hydrozoic acid precursor, trimethylsilyl azide in methanol.31 In these compounds, gold binds a monoanionic triazolate ligand through carbon. Reacting terminal alkynes with the corresponding phosphinegold(I) azide reagents led to the formation of the same compounds. Scheme 3.1.1 shows the employed reaction protocol. These reactions are uncatalyzed. Both the phosphinegold(I) azide and the gold(I) alkynyl are proposed as possible intermediate in these reactions. Nonhydrolyzable azides fail to react gold(I) alkynyls under identical conditions, and internal alkynes show no reactivity.

Scheme 3.1.1. Uncatalyzed Cycloaddition Reactions of Gold(I).

Cu(I)-catalyzed [3+2] cycloaddition reaction of azides and alkynes is the prototype of click chemistry. Its synthetic power and experimental ease have made this method widely used in various fields.2 While uncatalyzed thermal reactions produce a mixture of 1,4- and 1,5- isomers and some Ru(II)-catalyzed cycloadditions produce wholly or predominately 1,5-isomers,32, 33 this copper-catalyzed process selectively affords 1,4-regioisomeric products, Scheme 3.1.2.

Scheme 3.1.2. Cycloaddition Isomers.

The Cu(I) catalysts essentially work on the cycloaddition of organic azides and terminal alkynes. As a result, the triazolate compounds isolated from Cu(I)-catalyzed cycloadditon are usually not functionalized at the 4- position (R2 = H in

1,4-cycloaddition products, Scheme 3.1.2). Research efforts have been applied to synthesize functionalized 1,4-cycloaddition product from Cu(I)-catalyzed cycloadditions. To date only two successful examples34, 35 have been achieved with specially designed copper catalysts, as shown in Scheme 3.1.3. These two reactions

93 were carried out at elevated temperatures; longer reaction times, 24-48 h are also needed. The active internal alkyne is coincidentally a symmetric alkyne, 3-hexyne.

Diverse functionalization was not achieved. Ru(II)-catalyzed cycloaddition can produce triazolates from unstrained internal alkynes, but only generate 1,5 isomers.

Scheme 3.1.3. Examples of Cu(I) Catalyzed Cycloaddition of Benzyl Azide and an Internal

Alkyne.

The profusion of gold(I) internal alkynes and their reactivity towards hydrozoic acid to generate triazolates invite the investigation of their Cu(I)-catalyzed cycloaddition chemistry. Functionalizing the triazolate system with a gold(I) moiety may impart interesting properties. For example, binding gold(I) fragments to different substrates through triazolate provides an alternative for antitumor drug design.36

In this chapter, readily available copper(I) catalysts, [Cu(MeCN)4PF6] and CuI will be used to investigate the 1,3-dipolar cycloaddition chemistry of unstrained gold(I) internal alkynyls and benzyl azide. New compounds, including gold(I) alkynyls and gold(I) triazolates will be fully characterized using NMR, MS and 94 combustion elemental analysis. X-ray crystallography will be applied to those compounds that can give X-ray diffraction quality crystals. The structures will reveal the regioselectivity of the Cu(I)-catalyzed cycloaddition. UV-vis absorption and emission spectra will be collected for compounds bearing polycyclic aromatic functional groups, and the heavy atom effect of gold will be discussed. Control experiments will be performed by conducting the experiments with other Lewis-acid based catalysts or without catalyst. Reaction conditions will be compared with other

Cu(I)-catalyzed cycloaddition reactions of internal alkynyls and organic azides.

Different azide systems will also be investigated.

3.2. Results and discussions

Scheme 3.2.1 Reaction sequence of Cu(I)-Catalyzed Cycloaddition of Unstrained Gold(I) Internal Alkynyls and Benzyl Azide.

3.2.1. Synthesis and Characterization of Gold(I) Internal Alkynyls

As shown in Scheme 3.2.1, the synthesis of gold(I) triazolate complexes involves two steps. The first step is to synthesize the internal gold(I) alkynyl complexes. A strong base, NaOtBu, KOtBu or NaOMe was mixed with commercially available terminal alkynes in methanol. This solution was then added to a suspension of phosphine or N-heterocyclic carbene gold(I) chloride starting materials in methanol.

The resulting mixture was stirred vigorously at room temperature for 1-2 h (L=PPh3,

PCy3) or overnight (L=SIPr). The phosphine derivatives precipitate out of the solution, which was collected by filtration, followed by washing with cold methanol and pentane. The carbene complexes are soluble in methanol. After the reaction went to completion, the solvent, methanol was removed under rotary evaporation. The residue was then extracted with ether and filtered. Ether was then removed under rotary

96 evaporation. Triturating the residue with pentane led to the isolation of the products.

Using this method, 11 new gold(I) alkynyl complexes were synthesized. Scheme

3.2.2 collects the new gold(I) alkynyl complexes with their isolation yields.

Scheme 3.2.2. New gold(I) alkynyl complexes.

The conversion of the reaction was monitored by 31P{1H} (phosphine derivitatives) and 13C{1H} (SIPr derivitatives) NMR. Upon attachment of the gold(I) fragment to the triple bond, the 31P{1H} and 13C{1H} peaks of the phosphine and carbene carbon, respectively, all downfield shift compared to the starting material. However, the downfield shift is less than that observed when attaching gold(I) fragments directly to aryl groups, such as gold(I) naphthyl complexes as discussed in Chapter 2 of this thesis.

These gold(I) alkynyl compounds can be easily purified using crystallization.

Vapor diffusion of pentane into a concentrated benzene solution led to the formation

97 of crystals overnight. Compound 1-3 and 5-9 crystallize as colorless crystals.

Compound 10 crystallizes as yellow crystals. Compound 4 and compound 11 are red.

X-ray crystal structures were collected for compound 1, 3, 5, 9 and 10. Shown in

Figure 3.2.1 is the crystal structure of compound 9.37

Figure 3.2.1. Crystal structures (100 K) of compound 9. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon.

The structure shows the successful binding of the gold(I) fragment to the alkynyl group, and a linear two-coordinate geometry about gold. No aurophilic interaction or π-stacking was observed in the packing diagram. Table 3.2.1 37 collects the selected bond lengths. The Au-Ccarbene bond lengths are from 1.999(3) Å in 9 to

2.026 (3) Å in 10, and the Au-Calkynyl distances are from 1.988(2) Å in 11 to 1.994(4)

Å in 9. The C≡C bond lengths range from 1.171(5) Å in 9 to 1.221(4) Å in 10. The

98 bond angles in Table 3.2.2 show the Au–C≡C–R linkages to be essentially linear.

Compound Au–Ccarbene Au–Calkynyl C≡C 9 1.999(3) 1.994(4) 1.171(5) 10 2.026(3) 1.992(3) 1.221(4) 11 2.0132(19) 1.988(2) 1.204(3)

Table 3.2.1. Selected Interatomic Distances (Å) in Crystallographically Characterized Gold(I) Complexes.

Compound ∠Ccarbene–Au–Calkyne ∠Au–C≡C ∠ C≡C–R 9 179.4(5) 175.0(10) 176.3(7) 10 177.52(8) 174.1(2) 175.8(3) 11 174.23(8) 172.45(19) 175.8(3)

a The atom in boldface type lies at the vertex of the angle.

Table 3.2.2. Selected Interatomic Angles (°).a

200

503 nm SIPrAuC -2-naphthyl 50000 2 180 262 nm C=1.76E-5M Solvent: THF 160 40000 Ex: 314 nm 140 Emission Intensity (a.u.)

120

) 542 nm -1 30000 314 nm 302 nm 100 cm 346 nm -1 362 nm 80 (M

ε 20000 60

586 nm 10000 40

343 nm 20

0 0 250 300 350 400 450 500 550 600 650 700 750 Wavelength (nm)

Figure 3.2.2. Absorption and emission spectra for compound 9.

The alkynyl complexes bearing polycyclic aromatic hydrocarbon fragments are luminescent in fluid solvents at room temperature. Shown in Figure 3.2.2 is the combined absorption and emission spectra of compound 9. The absorption maxima occur at 302 nm and 314 nm. Two emission bands appear in the emission profile. The emission band with vibronic maxima at 346 nm and 362 nm is a mirror image of the absorption profile. The small Stokes shift indicates singlet parentage of this structured emission. The average peak-to-peak spacing of 1277 cm-1, suggests activation of ring-deforming vibrations. The second band spans from 500-600 nm, with vibronic maxima at 503 nm, 542 nm and 586 nm. The Stokes shift of the luminescence is about

11 000 cm-1. This lower-energy emission is oxygen-quenchable. It is assigned as an ethynylnaphthyl-centered triplet state emission.

Compound λex(nm) Em (nm) 1 310 331, 353, 497, 533 3 310 330, 345, 497, 533 4 285 305, 319, 533, 579 5 310 343, 359, 501, 540, 583 6 330 366, 385, 406, 529, 577 9 314 346, 362, 503, 542, 586 10 361 401, 650, 668, 708, 726

Table 3.2.3. Luminescence maxima (273 ± 2 K) of emissive compounds in THF solution.

Collected in Table 3.2.3 are the luminescence maxima of the emissive compounds. Both the singlet and triplet state emissions are strong for compound 1, 3

100 and 4-6. Compound 10 has a very strong singlet state emission band centering at 401 nm. The triplet state emission is barely observed when the concentration is about 10-5

M. Lowering the concentration would make the triplet state emission disappear. This pyrenyl-centered emission is obvious at liquid nitrogen temperature (77 K). Some selected absorption and emission spectra can be found in Appendix III.

3.2.2. Synthesis and Characterization of Gold(I) Triazolates

The second step shown in Scheme 3.2.1 is the copper(I) catalyzed Huisgen

[3+2] cycloaddition of gold(I) internal alkynyls with benzyl azide. 10 mol% of catalyst load was used. Typically, the catalyst [Cu(MeCN)4]PF6 was mixed with benzyl azide in acetonitrile (CH3CN) first, and the resulting mixture was stirred for about 5 min. A greenish solution was generated. To this solution was then added a

CH3CN solution of the gold(I) alkynyls. All the reagents were handled in a dry glove box. The mixture was then transferred out of the dry glove box, and stirred under Ar for 12 h. CH3CN was removed under rotary evaporation. An oily greenish residue was usually generated in this step. This residue was triturated with pentane in an ice bath to solidify. A brown-to-green solid was usually collected via filtration. This solid was then dissolved in benzene, and the benzene solution was filtered through celite several times to remove the green copper catalyst. Removing benzene generated an oily residue. Triturating this residue with pentane led to the isolation of crude products.

Compound 14 and 22 take the red color from ferrocene. Compound 24 has the red color of the free 1-ethynylnaphthalene. All other compounds were isolated as

101 off-white powders. The isolated solids were again dissolved in a minimum amount of benzene, and filtered through celite. Vapor diffusion of pentane into the benzene solutions, or layering pentane on top of the solutions led to the isolation of crystals.

Table 3.2.4 collects all the new gold(I) triazolates with their isolation yields.

Compound 12 has the best isolation yield, up to 96%, because the isolation and purification are relatively easier than other compounds. Most of the compounds are difficult to purify. Contamination by the copper(I) catalyst was obvious as indicated by the greenish color. Several crystallization cycles are often necessary.

Table 3.2.4. Synthesis of Gold(I) Triazolate Complexes.

102

The presence of Cu(I) proves to be necessary for the reaction to happen.

Attempts at [3 + 2] cycloaddition of gold(I) alkynyls catalyzed by Lewis-acid based catalysts, such as (THT)AuCl (THT = tetrahydrothiophene), AgOTf (OTf = triflate),

5 or Cp*RuCl(COD) (Cp* = η -C5Me5, COD = (1Z,5Z)-cycloocta-1,5-diene) produced no discernable product; starting materials were recovered. Another copper(I) source,

CuI, is efficient in catalyzing the reaction and is easier to remove. No reaction happens when the copper(I) catalyst is not present. Reactions with phenyl azide yield no product. Another azide starting material, 1-azidoadamantane, can also undergo copper-catalyzed cycloaddition with gold(I) alkynyls, Scheme 3.2.3. However, gold(I) alkynyls with strong electron withdrawing functional groups, such as an ester group, are required to facilitate the reaction, and the isolation yields are low.38

Scheme 3.2.3. Cu(I)-Catalyzed Cycloaddition of Gold(I) Alkynyls with 1-Azidoadamantane.

The formation of the triazolates can be easily diagnosed by 1H NMR through a downfield shift of the benzylic hydrogen resonances. As an example, the resonance of

benzylic protons of compound 12 occurs at 5.65 ppm in C6D6 relative to tetramethylsilane. The resonance of the same protons of the benzyl azide occurs at

3.66 ppm. The selected 1H NMR spectra for the synthesized compounds are shown in

Appendix II.

103

Shown in Figure 3.2.3 is a representative crystal structure, compound 12. The structure shows a linear, two-coordinate geometry around gold, and is the

1,4-cycloaddition isomer. The functional groups from both the gold(I) internal alkynyl and the benzyl azide are maintained. The gold-triazolato carbon bond distance is

2.015(3) Å, and is nearly identical to the Au–Ccarbene length at 2.018(3) Å. For comparison, the gold-carbon bond in (Ph3P)Au(4-tolyltriazole) measures 2.027(5)

Å,31 in which a triazole nitrogen binds hydrogen, rather than an organic substituent. In the structure of a two-coordinate (triphenylphosphine)gold(I) allenoate complex,

Hammond and co-workers report a 2.036(5) Å C–Au bond.39 Such bond lengths are expected for gold(I)-carbon single bonds.40, 41 Gold(I) is two-coordinate and virtually linear; the Ctriazolate–Au–Ccarbene angle is 175.06(13)°. The triazolate and naphthyl ring systems are nearly coplanar; the dihedral angle between their (non-hydrogen-atom) mean planes is 5.50°. The triazolate linker moves gold nearer the naphthyl fragment than in its alkynyl precursor. In 12, gold is 3.593(4) Å from the nearest naphthyl carbon atom; in (SIPr)Au(2-ethynylnaphthalene) (9), it is 4.621(5) Å away.26 Metric parameters of 11 are similar.

Shown in Table 3.2.5 are the selected bond lengths and bond angles of the other crystallographically characterized gold(I) complexes. The Ctriazolate–Au–Ccarbene linkages are closer to be linear than Ctriazolate–Au–P. The smallest angle appears in compound 15, 171.56(6)°. Au–Ctriazolate bond lengths tend to be slightly shorter than the Au–Ccarbene bonds. All the bond lengths appear in the expected ranges.

104

Figure 3.2.3. Crystal Structure (100 K) of compound 12. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon.

13 14 15 16 17 18 20

Au–Ctriazolate 2.000(8) 2.022(4) 2.033(2) 2.021(0) 2.034(2) 2.028(4) 2.050(3)

Au–Ccarbene 2.007(12) 2.023(4)

Au–P 2.2762(5) 2.2746(11) 2.27976) 2.2720(12) 2.307(2)

∠Ctriazolate–Au–Ccarbene 178.7(4) 178.79(17)

∠Ctriazolate–Au–P 171.56(6) 178.74(12) 178.25(6) 177.59(13) 176.00(8) a The atom in boldface type lies at the vertex of the angle.

Table 3.2.5. Selected Interatomic Distances (Å) and Interatomic Angles (°)a in Crystallographically Characterized Gold(I) Complexes.

The synthesized triazolate complexes bearing polycyclic aromatic hydrocarbon fragments are luminescent. A typical example is compound 12. A combined absorption and emission spectrum of 12 is shown in Figure 3.2.4. The absorption ranges from 250-400 nm, with the absorption maximum occurring at 312 nm, with ε =

16 600 M-1cm-1. A shoulder appears at 325 nm. Higher-energy absorption peaks occur between 250 nm and 275 nm.

105

40000

498 nm

30000 (a.u.) Intensity Emission 536 nm ) ? 20000 cm

? 312 nm 383 nm (M ε 579 nm 10000

0 250 300 350 400 450 500 550 600 650 700 750 Wavelength (nm)

Figure 3.2.4. Room-temperature absorption (blue) and emission spectra (red, 312-nm excitation) of 12 in THF.

Exciting 12 at 312 nm elicits dual emission at room temperature. The higher energy emission appears around 383 nm; the vibronic structure is partially resolved.

This emission band is not sensitive to the presence of oxygen, which is attributed to the ligand-centered fluorescence. A lower-energy, O2-quenchable emission band appears near 475 nm. The vibronic structure is clearly resolved with maxima at 498 nm, 536 nm, and 579 nm, corresponding to an average separation of 1400 cm-1. These vibronic spacings suggest that ring-deformation modes are activated in the excited states. Similar emission structure occurs in the triplet-state emission of naphthalene embedded in sandwich adducts with trinuclear gold,42, 43 and in the free hydrocarbon.44 Absorption and emission spectra for all emissive compounds are listed in Appendix III.

106

Compound T Emax(nm) λem τ ϕem (K) (nm)a (ms) 12 295 497 0.00092 12 77 495 19.1 21 295 522 0.0014 21 77 515 0.260 22 295 530 0.0025 22 77 540 0.277 23 295 532 0.0016 23 77 490 5.06 24 295 531 0.0028 24 77 540 0.401

a Wavelength at which emission lifetime data were collected

Table 3.2.6. Emission lifetimes τ and quantum yields φem of luminescent compounds in 2-MeTHF solution (room temperature) or glass (77 K).

Time-resolved measurements at 77 K find that the emissions near 475 nm last from hundreds of microseconds to tens of milliseconds. Table 3.2.6 collects luminescence lifetimes and quantum yields data. Emission persist the longest for 12; its lifetime is 19.1 ms (77 K). The long lifetimes of luminescence combined with the oxygen-quenchable feature of this emission band indicate triplet-state luminescence, showing that the heavy atom effect of gold affects the excited states of the polycyclic aromatics even with a triazolate spacer present. Quantum yields are in a range typical of ligand-centered luminescence. When comparing with the gold(I) alkynyls, the phosphorescence quantum yields of the triazolates tend to be lower.

107

3.3. Conclusions

In this chapter, gold(I) triazolate complexes were successfully synthesized by reacting internal gold(I) alkynyls with benzyl azide, through a copper(I)-catalyzed click chemistry pathway. The reactions proceed with 1,4-regioselectivity, and the triazolate products retain the substituents from both the azide and alkynyls.

In the synthesis, 11 new gold(I) alkynyl and 13 new gold(I) triazolate complexes were successfully synthesized. All of them were characterized using NMR, MS, combustion elemental analysis, UV-vis, fluorescence and X-ray crystallography when diffraction quality crystals were available. Intermolecular aurophilic interactions were excluded for these compounds by observing the packing diagram of crystal structures.

The gold(I) alkynyls and gold(I) triazolates with photoactive substituents have dual luminescence. Both singlet and triplet-state emissions are observed. The phosphorescence suggests a pseudo-external heavy-atom effect, where gold promotes intersystem crossing to reach an emissive, ligand-centered triplet state. The vibronic splitting of the emission patterns suggest a ring deformation modes activated in the lowest triplet state.

The results demonstrate that the internal gold(I) alkynyls support copper-catalyzed cycloaddition with organic azides. Control experiments with other

Lewis-acid based catalysts or without catalyst show no reactions, and starting materials were isolated. CuI works as efficiently as [Cu(MeCN)4]PF6. These copper(I) catalysts easily contaminate the products, and are hard to remove. Looking for new

108 efficient copper catalysts which can be separated from the products will be the desired future research direction. Catalysis efficiency will be studied by varying the loading of the catalysts, and turnover number will be calculated. When no catalyst is present, the reaction cannot proceed, showing that Au(I) itself has no catalytic activity towards the cycloaddition reaction.

109

3.4. Experimental

3.4.1. Reagents

Unless otherwise specified, all commercially available reagents were used as received without further purification. PPh3AuCl and PCy3AuCl were synthesized by a modified literature procedure.45 SIPrAuCl and known gold(I) alkynyls were synthesized following literature procedures.26, 46

3.4.2. Instrumentation

NMR Spectroscopy. NMR spectra (1H, 13C{1H}, and 31P{1H}) were recorded on a Varian AS-400 spectrometer. Chemical shifts are reported in parts-per-million

1 13 1 31 1 relative to Si(CH3)4 ( H, C{ H}), or 85% aqueous H3PO4 ( P{ H}).

Optical Properties Characetrization. UV-vis spectra were collected on a Cary

500 spectrophotometer in degassed HPLC grade solvents. Fluorescence measurements were done with a Cary Eclipse Spectrophotometer at room temperature.

All the samples were purged with argon for at least 15 min before the luminescence measurement. Steady state emission spectra were recorded at room temperature on an automated Photon Technology International (PTI) QM 4 fluorimeter equipped with a

150-W Xe arc lamp and a Hamamatsu R928 photomultiplier tube. Excitation light was excluded with appropriate glass filters. Sample solutions were added to a quartz

110

EPR tube, freeze pump thaw degassed (4 cycles, 1 × 10–5 Torr) and flame sealed. Low temperature emission spectra were recorded in rigid solvent glass at 77 K by immersion of the sealed EPR tubes into a liquid nitrogen-filled dewar.

X-Ray Structure Determinations. Single crystal X-ray data were collected on a

Bruker AXS SMART APEX CCD diffractometer using monochromatic Mo Kα radiation with the omega scan technique. The unit cells were determined using

SMART47 and SAINT+. Data collection for all crystals was conducted at 100 K

(-173.5°C). All structures were solved by direct methods and refined by full matrix least squares against F2 with all reflections using SHELXTL. Refinement of extinction coefficients was found to be insignificant. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in standard calculated positions and all hydrogen atoms were refined with an isotropic displacement parameter 1.2 times that of the adjacent carbon.

3.4.3. Synthesis of New Gold(I) Alkynyls and Triazolates

[(PPh3)Au(4-biphenylethynyl)] (1). Used KOtBu (46 mg, 0.41 mmol),

4-ethynylbiphenyl (72 mg, 0.41 mmol), and (PPh3)AuCl (102 mg, 0.21 mmol). No

1 recrystallization of the product was required. Yield: 101 mg (78%). H NMR (C6D6):

δ 7.89 (d, 4-biphenylethynyl, 2H, J = 8.4 Hz), 7.38 (d, 4-biphenylethynyl, 2H, J = 7.2

Hz), 7.33 (d, 4-biphenylethynyl, 2H, J = 8.0 Hz), 7.20-7.30 (m, 6H), 7.15-7.19 (m,

2H), 7.08 (t, para-4-biphenylethynyl, 1H, J = 7.2 Hz), 6.84-6.98 (m, 9H) ppm. 31P{1H}

-1 NMR (C6D6): δ 42.6 (s) ppm. IR (KBr): 2109 (w, υC≡C) cm . Anal. Calcd. for

111

C32H24AuP: C, 60.39; H, 3.80. Found: C, 60.51; H, 3.95.

[(PPh3)Au(3-thienylethynyl)] (2). Used KOtBu (90 mg, 0.9 mmol ),

3-ethynylthienyl (88.5 mg, 0.8 mmol) and PPh3AuCl (0.2815g, 0.6 mmol).Yield:

1 0.2510 g (91%). H NMR (C6D6): δ 7.36 (d, 1H, J = 2.8 Hz, 3-thienyl), 7.31 (d, 1H, J

= 4.8 Hz, 3-thienyl), 7.22 (dd, 6H, J = 12.4 Hz, 7.2 Hz, (C18H15)P)), 6.85-6.96 (m,

31 1 9H, (C18H15)P)), 6.72 (dd, 1H, J = 4.8 Hz, 2.8 Hz, 3-thienyl). P{ H} NMR (C6D6):

-1 42.4 ppm. IR (KBr): 2110 (w, υC≡C) cm Anal. Calcd. for C24H18AuPS: C, 50.89; H,

3.20. Found, C, 50.70; H, 3.29.

[(PCy3)Au(4-biphenylethynyl)] (3). Used NaOtBu (49 mg, 0.51 mmol),

4-ethynylbiphenyl (90 mg, 0.50 mmol), and (PCy3)AuCl (133 mg, 0.26 mol).Yield:

1 102 mg (60%). H NMR (C6D6): δ 7.83 (d, 4-ethynylbiphenyl, 2H, J = 8.0 Hz), 7.36

(d, 4-ethynylbiphenyl, 2H, J = 7.6 Hz), 7.30 (d, 4-ethynylbiphenyl, 2H, J = 8.0 Hz),

7.13-7.17 (m, 2H), 7.07 (t, para-4-ethynylbiphenyl, 1H, J = 7.2 Hz), 0.84-1.80 (m,

31 1 33H, C6H11) ppm. P{ H} NMR (C6D6): δ 56.7 (s) ppm. IR (KBr): 2109 (w, υC≡C)

-1 cm . Anal. Calcd. for C32H42AuP: C, 58.71; H, 6.47. Found: C, 58.45; H, 6.39.

[(PCy3)Au(1-naphthylethynyl)] (4). Used KOtBu (37 mg, 0.33 mmol),

1-ethynylnaphthalene (50 mg, 0.33 mmol), and (PCy3)AuCl (84 mg, 0.16 mmol).

1 Yield: 66 mg (64%). H NMR (C6D6): δ 9.29 (s, 1-naphthyl, 1H, J = 8.4 Hz), 8.00 (d,

1-naphthyl, 1H, J = 6.8 Hz), 7.59 (d, 1-naphthyl, 1H, J = 8.0 Hz), 7.47 (d, 1-naphthyl,

112

1H, J = 8.0 Hz), 7.30 (t, 1-naphthyl, 1H, J = 7.6 Hz), 8.00 (t, 1-naphthyl, 1H, J = 7.6

Hz), 7.10-7.14 (m, 1-naphthyl, 1H, J = 6.8 Hz), 0.89-1.80 (m, 33H, P(C6H11)3) ppm.

31 1 -1 P{ H} NMR (C6D6): δ 56.5 (s) ppm. IR (KBr): 2107 (w, υC≡C) cm . Anal. Calcd. for

C30H40AuP: C, 57.32; H, 6.41. Found: C, 57.48; H, 6.21.

[(PCy3)Au(2-naphthylethynyl)] (5). Used KOtBu (42 mg, 0.37 mmol),

2-ethynylnaphthalene (57 mg, 0.37 mmol), and (PCy3)AuCl (96 mg, 0.19 mmol) and a total of only 4 mL of methanol (2 mL for alkynyl solution, 2mL for gold suspension).

1 Yield: 102 mg (87%). H NMR (C6D6): δ 8.26 (s, 2-naphthyl, 1H), 7.89 (dd,

2-naphthyl, 1H, J = 1.6, 8.4 Hz), 7.40-7.50 (m, 2-naphthyl, 3H), 7.09-7.14 (m,

31 1 2-naphthyl, 2H), 0.89-1.80 (m, 33H, P(C6H11)3) ppm. P{ H} NMR (C6D6): δ 56.7 (s)

-1 ppm. IR (KBr): 2109 (w, υC≡C) cm . Anal. Calcd. for C30H40AuP: C, 57.32; H, 6.41.

Found: C, 57.13; H, 6.36.

[(PCy3)Au(9-phenanthrylethynyl)] (6). Used NaOtBu (45 mg, 0.47 mmol),

2-ethynylphenanthrene (94 mg, 0.47 mmol), and (PCy3)AuCl (119 mg, 0.23 mmol).

1 Yield: 111 mg (71%). H NMR (C6D6): δ 9.46 (d, 9-phenanthryl, 1H, J = 7.6 Hz),

8.44 (d, 9-phenanthryl, 1H, J = 7.6 Hz), 8.38 (d, 9-phenanthryl, 1H, J = 8.4 Hz), 8.28

(s, 9-phenanthryl, 1H), 7.46 (q, 9-phenanthryl, 2H, J = 7.2 Hz), 7.38 (t, 9-phenanthryl,

1H, J = 7.6 Hz), 7.30 (t, 9-phenanthryl, 1H, J = 7.2 Hz), 7.23 (t, 9-phenanthryl, 1H, J

31 1 = 7.6 Hz), 0.89-1.80 (m, 33H, P(C6H11)3) ppm. P{ H} NMR (C6D6): δ 56.6 (s) ppm.

-1 -1 -1 IR (KBr): 2102 (w, υC≡C) cm . UV-Vis (THF): λ (ε, M cm ) 278 (2284) , 316 nm

113

(2291), 331 nm (2852). Anal. Calcd. for C34H42AuP: C, 60.17; H, 6.24. Found: C,

59.89; H, 5.99.

[(PCy3)Au(3-thienylethynyl)] (7). Used KOtBu (56 mg, 0.50 mmol),

3-ethynylthiophene (54 mg, 0.50 mmol), and (PCy3)AuCl (128 mg, 0.25 mmol). The

1 crude material was analytically pure. Yield: 115 mg (79%). H NMR (C6D6): δ 7.31

(dd, 3-thienyl, 1H, J = 1.2, 2.8 Hz), 7.27 (dd, 3-thienyl, 1H, J = 1.2, 4.8 Hz), 6.70 (dd,

31 1 3-thienyl, 1H, J = 4.8, 2.8 Hz), 0.78-1.75 (m, 33H, P(C6H11)3) ppm. P{ H} NMR

-1 (C6D6): δ 56.6 (s) ppm. IR (KBr): 2116 (w, υC≡C) cm . Anal. Calcd. for C24H36AuPS:

C, 49.30; H, 6.21. Found: C, 49.49; H, 6.30.

[(SIPr)Au(tert-butylethynyl)] (8). Used NaOtBu (100 mg, 1.0 mmol),

4-ethynyl-tert-butyl (85 mg, 1.0 mmol) and SIPrAuCl (0.3238 g, 0.5 mmol).Yield:

1 0.2924 g (79%). H NMR (C6D6): δ 7.09 (t, 2H, J = 7.6 Hz, CH aromatic on SIPr),

6.97 (d, 4H, J = 7.6 Hz, CH aromatic on SIPr), 3.08 (s, 4H, CH imidazole), 2.94

(septet, 4H, J = 6.8 Hz CH(CH3)2), 1.50 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.15 (s, 9H,

-1 C(CH3)3), 1.13 (d, 12H, J = 6.8 Hz, CH(CH3)2). IR (KBr): 2110 (w, υC≡C) cm . Anal.

Calcd. for C33H47AuN2: C, 59.27, H, 7.08, N 4.19. Found, C, 59.29, H, 7.28, N, 4.16.

[(SIPr)Au(2-naphthylethynyl)] (9). Used NaOtBu (62 mg, 0.6 mmol),

2-ethynylnaphthyl (98.1 mg, 0.6 mmol) and SIPrAuCl (0.2010 g, 0.3 mmol). Yield:

1 0.2310 g (79%). H NMR (C6D6): δ 7.72 (s, 1H, 2-naphthyl), 7.39-7.42 (m, 1H,

114

2-naphthyl), 7.35-7.37 (m, 1H, 2-naphthyl), 7.27-7.29 (m, 1H, 2-naphthyl), 7.18-7.20

(m, 3H, 2-naphthyl and CH aromatic on SIPr), 7.01-7.05 (m, 6H, 2-naphthyl and CH aromatic on SIPr), 3.13 (s, 4H, CH imidazole), 2.99 (septet, 4H, J = 6.8 Hz

CH(CH3)2), 1.55 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.17 (d, 12H, J = 6.8 Hz,

-1 -1 -1 CH(CH3)2). IR (KBr): 2107 (s, υC≡C) cm UV-Vis (THF): λ (ε, M cm ) 262 (48152),

302 (26470), 314 (29748), 343 (5342) nm. Anal. Calcd. for C39H45AuN2: C, 63.41; H,

6.14; N, 3.79. Found, C, 63.37; H, 5.90; N, 3.76.

[(SIPr)Au(1-pyrenylethynyl)] (10). Used NaOtBu (34.7 mg, 0.4 mmol),

1-ethynylpyrenyl (82 mg, 0.4 mmol) and SIPrAuCl (0.2046 g, 0.3 mmol). Yield,

0.1555 g (58%). 1H NMR (C6D6): δ 9.01 (2, 1H, J = 9.2 Hz, 1-pyrenyl), 7.97 (d, 1H,

J = 8.4 Hz, 1-pyrenyl), 7.78 (dd, 2H, J = 12 Hz, 7.6 Hz, 1-pyrenyl), 7.51-7.64 (m, 5H,

1-pyrenyl), 7.20 (t, 2H, J = 8 Hz, CH aromatic on SIPr), 7.06 (d, J = 8 Hz, CH aromatic on SIPr), 3.16 (s, 4H, CH imidazole), 3.04 (septet, 4H, J = 6.8 Hz

CH(CH3)2), 1.61 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.20 (d, 12H, J = 6.8 Hz,

-1 -1 -1 CH(CH3)2). IR (KBr): 2087.66 (s, υC≡C) cm UV-Vis (THF): λ (ε, M cm ) 280

(21971), 290 (26258), 345 (14722), 361 (31563), 383 (42963), 392 (16785) nm. The identity of the product was authenticated by X-ray crystallography.

[(SIPr)Au(ferrocenylethynyl)] (11). Used NaOtBu (65 mg, 0.68 mmol ),

3-ethynylthienyl (141.2 mg, 0.68 mmol) and SIPrAuCl (0.2217 g, 0.36 mmol).Yield:

1 0.2190 g (75%). H NMR (C6D6): δ 7.12 (t, 2H, J = 7.6 Hz, CH aromatic on SIPr),

115

7.00 (d, J = 7.6 Hz, CH aromatic on SIPr), 4.21, (s, 2H, ferrocenyl), 3.91 (s, 5H ferrocenyl), 3.70 9s, 2H, ferrocenyl), 3.10 (s, 4H, CH imidazole), 2.95 (septet, 4H, J

= 6.8 Hz CH(CH3)2), 1.51 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.15 (s, 9H, C(CH3)3),

-1 1.13 (d, 12H, J = 6.8 Hz, CH(CH3)2). IR (KBr): 2102 (w, υC≡C) cm Anal. Calcd. for

C39H47AuFeN2: C, 58.80; H, 5.95; N, 3.52. Found, C, 58.89 ; H, 5.85 ; N, 3.49.

[(SIPr)Au(1-benzyl-4-(2-naphthyl)triazolato)] (12). In a nitrogen-filled glove box, [(SIPr)Au(2-ethynylnaphthalene)] (96.1 mg, 0.13 mmol) was suspended in 5 mL acetonitrile. To this was added the mixture of benzyl azide (48 mg, 0.36 mmol) and

[Cu(MeCN)4]PF6 (4.6 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h. Solvent was removed under rotary evaporation. The remaining residue was extracted with benzene and filtered through celite to yield a slightly yellow solution. Benzene was removed under rotary evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration. Crystallization by diffusing pentane into a benzene

1 solution yielded colorless crystals. Yield: 103 mg, 96%. H NMR (C6D6): δ (ppm)

9.12 (s, 1H), 8.16 (dd, 1H, J = 8.4 Hz, 2 Hz, 2-naphthyl), 7.83 (d, 1H, J = 7.6 Hz,

2-naphthyl), 7.60 (d, 1H, J = 8 Hz, 2-naphthyl), 7.43 (d, 1H, J = 8.8 Hz, 2-naphthyl),

7.30 (t, 1H, J = 6.8 Hz, 2-naphthyl), 7.20-7.23 (m, 3H, 2-naphthyl, CH aromatic on

SIPr), 7.00-7.03 (m, 3H, CH aromatic on benzyl), 6.98 (d, 4H, J = 8 Hz, CH aromatic on SIPr), 6.78-6.80 (m, 2H, CH aromatic on benzyl), 5.02 (s, 2H, CH2-benzyl), 3.12

(s, 4H, CH imidazole), 2.90 (septet, 4H, J = 7.2 Hz CH(CH3)2), 1.25 (d, 12H, J = 6.8

116

-1 -1 Hz, CH(CH3)2), 1.11 (d, 12H, J = 6.8 Hz, CH(CH3)2). UV-Vis (THF): λ (ε, M cm )

257 (30660), 267 (28170), 312 (16832) nm. Anal. Calcd. for C46H52AuN5: C, 63.37; H,

6.01; N, 8.03. Found: C, 63.58; H, 5.91; N, 8.07.

[(SIPr)Au(1-benzyl-4-tert-butyltriazolato)] (13). In a nitrogen-filled glove box,

[(SIPr)Au(tert-butylethynyl)] (75.7 mg, 0.11 mmol) was dissolved in 5 mL acetonitrile. To this was added the mixture of benzyl azide (44 mg, 0.33 mmol) and

[Cu(MeCN)4]PF6 (4.1 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h. Acetonitrile was then removed under rotary evaporation. The remaining residue was first triturated with pentane to yield a greenish powder. The powder was then redissolved in benzene and filtered through celite. Benzene was removed from the filtrate by rotary evaporation. Pentane was used to triturate the residue, and an off-white powder was collected by filtration.

Crystallization by layering pentane onto a benzene solution yielded colorless crystals.

1 Yield: 77.2 mg, 85%. H NMR (C6D6): δ (ppm) 7.11 (d, 2H, J = 7.6 Hz, CH aromatic

SIPr), 6.98-6.99 (m, 3H, CH aromatic on benzyl), 6.96 (d, 4H, J = 8 Hz, CH aromatic

SIPr), 6.77-6.79 (m, 2H, CH aromatic on benzyl), 5.06 (s, 2H, CH2-benzyl), 3.15 (s,

4H, CH imidazole), 2.89 (septet, 4H, J = 7.2 Hz, CH(CH3)2), 1.38 (s, 9H, t-butyl),

1.33 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.13 (d, 12H, J = 6.8 Hz, CH(CH3)2). Anal.

Calcd. for C40H54AuN5: C, 59.92; H, 6.79; N, 8.73. Found: C, 60.06; H, 6.74; N, 8.48.

117

[(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)] (14). In a glove box,

[(SIPr)Au(ferrocenylethynyl)] (91.8 mg, 0.11 mmol) was suspended in 5 mL acetonitrile. To this was added the mixture of benzyl azide (44 mg, 0.33 mmol) and

[Cu(MeCN)4]PF6 (4.1 mg 10 mol%) under stirring. The mixture was then stirred under Ar at RT for 12 h. The resultant solution was put under rotavap and acetonitrile was taken off. The remaining residue was first triturated with pentane to yield a dark orange powder. The powder was then redissolved in benzene and filtered through celite. The filtrate was put under rotary evaporation to remove benzene. Pentane was used to triturate the resultant residue, and an orange powder was collected by filtration.

Crystallization by layering pentane onto a benzene solution yielded red crystals. Yield:

1 70 mg, 66%. H NMR (C6D6) δ (ppm) 7.20 (t, 2H, J = 7.2 Hz, CH aromatic on SIPr),

7.00-7.02 (m, 7H, CH aromatic on SIPr and benzyl), 6.72-6.74 (m, 2H, CH aromatic on benzyl), 5.05 (s, 2H, CH2-benzyl), 4.66 (s, 2H, ferrocenyl), 4.11 (s, 5H, ferrocenyl),

4.01 (s, 2H, ferrocenyl) 3.16 (s, 4H, CH imidazole), 2.90 (septet, 4H, J = 7.2 Hz,

CH(CH3)2), 1.34 (d, 12H, J = 6.8 Hz, CH(CH3)2), 1.14 (d, 12H, J = 6.8 Hz,

+ + CH(CH3)2). MS (ES ): Calcd. m/z = 929.3395 (M ); Found m/z = 929.3547.

[(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)] (15). In a nitrogen-filled glove box, [(PPh3)Au(carboxymethyl-ethynyl)] (84 mg, 0.15 mmol) was dissolved in 5 mL acetonitrile. To this was added the mixture of benzyl azide (60 mg, 0.45 mmol) and

[Cu(MeCN)4]PF6 (5.6 mg, 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h, after which the solvent was removed

118 through evaporation. The remaining residue was first triturated with pentane to yield a greenish brown powder. The powder was then redissolved in benzene and filtered through celite. Benzene was removed by rotary evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration.

Crystallization by layering pentane onto a benzene solution yielded colorless crystals.

1 Yield: 67 mg, 58%. H NMR (C6D6): δ (ppm) 7.33-7.35 (m, 6H, CH aromatic), 7.07

(d, 3H, J = 7.6 Hz, CH aromatic), 6.84-66.97 (m, 14H, CH aromatic), 5.36 (s, 2H,

31 1 CH2-benzyl), 3.68 (s, 3H, CO2CH3). P{ H} NMR (C6D6): δ 43.3(s) ppm. IR (KBr):

-1 + 1712 (vs, υC=O) cm . HR-MS (ES+): Calcd. m/z = 676.1428 (M+H) ; Found m/z =

676.1441. Anal. Calcd. for C29H25AuN3O2P: C, 51.57; H, 3.73; N, 6.22. Found: C,

51.67; H, 3.75; N, 6.21.

[(PPh3)Au(1-benzyl-4-phenyltriazolato)] (16). In a nitrogen-filled glove box,

[(PPh3)Au(phenylethynyl)] (71 mg, 0.13 mmol) was dissolved in 5 mL acetonitrile.

To this was added the mixture of benzyl azide (51 mg, 0.38 mmol) and

[Cu(MeCN)4]PF6 (4.7 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h. Solvent was removed by rotary evaporation.

The remaining residue was first triturated with pentane to yield a greenish brown powder. The powder was then redissolved in benzene and filtered through celite.

Benzene was removed from the filtrate by rotary evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration.

Crystallization by layering pentane onto a benzene solution yielded colorless crystals.

119

1 Yield: 60 mg, 67%. H NMR (C6D6): δ (ppm) 8.81 (d, 2H, J = 7.2 Hz, CH aromatic),

7.27 (t, 2H, J = 7.6 Hz, CH aromatic), 6.90-7.13 (m, 21H, CH aromatic), 5.50 (s, 2H,

31 1 CH2-benzyl). P{ H} NMR (C6D6): δ 43.9(s) ppm. HR-MS (ES+): Calcd. m/z =

+ 694.1686 (M+H) ; Found m/z = 694.1670. Anal. Calcd. for C33H27AuN3P: C, 57.15;

H, 3.92; N, 6.06. Found: C, 57.05; H, 3.94; N, 6.05.

[(PPh3)Au(1-benzyl-4-(4-tolyl)triazolato)] (17). In a nitrogen-filled glove box,

[(PPh3)Au(4-tolylethynyl)] (66 mg, 0.11 mmol) was dissolved in 5 mL acetonitrile. To this was added the mixture of benzyl azide (44 mg, 0.33 mmol) and [Cu(MeCN)4]PF6

(4.0 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h. Acetonitrile was removed by rotary evaporation. The remaining residue was first triturated with pentane to yield a greenish brown powder. The powder was then redissolved in benzene and filtered through celite. Benzene was removed by evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration. Crystallization by layering pentane onto

1 a benzene solution yielded colorless crystals. Yield: 48 mg, 58%. H NMR (C6D6): δ

(ppm) 8.23 (d, 2H, J = 6.8 Hz, CH aromatic), 7.16 (s, 2H, CH aromatic), 6.92-7.10 (m,

31 1 20H, CH aromatic), 5.50 (s, 2H, CH2-benzyl), 2.17 (s, 3H, CH3). P{ H} NMR

+ (C6D6): δ 44.0 (s) ppm. HR-MS (ES+): Calcd. m/z =708.1843 (M+H) ; Found m/z =

708.1860. Anal. Calcd. for C34H29AuN3P: C, 57.72; H, 4.13; N, 5.94. Found: C, 57.57;

H, 4.21; N, 5.79.

120

[(PPh3)Au(1-benzyl-4-(4-fluorophenyl)triazolato)] (18). In a nitrogen-filled glove box, [(PPh3)Au(4-fluorophenylethynyl)] (87.7 mg, 0.15 mmol) was dissolved in

5 mL acetonitrile. To this was added the mixture of benzyl azide (60 mg, 0.45 mmol) and [Cu(MeCN)4]PF6 (5.6 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h. The resultant precipitate was collected by decanting the solution carefully. Solvent was removed from the solution under rotary evaporation. The remaining residue was first triturated with pentane to yield a greenish brown powder. The powder was then redissolved in benzene and filtered through celite. Benzene was removed by rotary evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration. The original white precipitate and the powder were combined as the product.

Crystallization by layering pentane onto a benzene solution yielded colorless crystals.

1 Yield: 72 mg, 66%. H NMR (C6D6): δ (ppm) 8.71 (dd, 2H, J = 8 Hz, 5.6 Hz, CH

31 1 aromatic), 6.89-7.13 (m, 22H, CH aromatic), 5.49 (s, 2H, CH2-benzyl). P{ H} NMR

+ (C6D6): δ 44.1(s) ppm. HR-MS (ES+): Calcd. m/z = 712.1592 (M+H) ; Found m/z =

712.1591. Anal. Calcd. for C33H26AuN3PF: C, 55.71; H, 3.68; N, 5.91. Found: C,

55.83; H, 3.44; N, 5.82.

[(PPh3)Au(1-benzyl-4-(3-thienyl)triazolato)] (19). In a nitrogen-filled glove box, [(PPh3)Au(3-thienylethynyl)] (68.7 mg) was dissolved in 5 mL acetonitrile. To this was added the mixture of benzyl azide (49 mg) and [Cu(MeCN)4]PF6 (4.5 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature

121 for 12 h. Acetonitrile was removed by rotary evaporation. The remaining residue was first triturated with pentane to yield a greenish powder. The powder was then redissolved in benzene and filtered through celite. Benzene was removed by rotary evaporation. Pentane was used to triturate the resultant residue, and an off-white powder was collected by filtration. Crystallization by layering pentane onto a benzene

1 solution yielded colorless crystals. Yield: 56 mg, 66%. H NMR (C6D6): δ (ppm) 8.32

(dd, 1H, J = 4 Hz, 1.2 Hz, 3-thienyl), 8.22 (dd, 1H, J = 2.8 Hz, 1.2 Hz, 3-thienyl),

7.18 (s, 2H, 3-thienyl, CH aromatic) 7.10-7.11 (m, 3H, CH aromatic), 6.90-7.00 (m,

31 1 16H, CH aromatic, P(C6H5)3), 5.48 (s, 2H, CH2-benzyl). P{ H} NMR (C6D6): δ 44.3

(s) ppm. HR-MS (ES+): Calcd. m/z = 700.1251 (M+H)+; Found m/z = 700.1278.

Anal. Calcd. for C31H25AuN3PS: C, 53.22; H, 3.60; N, 6.01. Found: C, 53.37; H, 3.38;

N, 5.81.

[(PPh3)Au(1-benzyl-4-ferrocenyltriazolato)] (20). (PPh3)Au(ethynylferrocene)

(77 mg, 0.11 mmol) was suspended in 5 mL acetonitrile. To this was added the mixture of benzyl azide (45 mg, 0.33 mmol) and [Cu(MeCN)4]PF6 (4.3 mg 10 mol%) under stirring. The mixture was then stirred under argon at room temperature for 12 h.

Acetonitrile was removed by rotary evaporation. The remaining residue was first triturated with pentane to yield a dark orange powder. The powder was then redissolved in benzene and filtered through celite. Benzene was then removed by rotary evaporation. Pentane was used to triturate the resultant residue, and an orange powder was collected by filtration. Crystallization by layering pentane onto a benzene

122

1 solution yielded orange crystals. Yield: 68 mg, 73%. H NMR (C6D6): δ (ppm)

7.26-7.31 (m, 8H, CH aromatic), 6.90-7.10 (m, 12H, CH aromatic), 5.52 (s, 2H,

CH2-benzyl), 5.41 (t, 2H, J = 1.6Hz, ferrocenyl), 4.15 (t, 2H, J = 1.6 Hz, ferrocenyl),

31 1 4.10 (s, 5H, ferrocenyl). P{ H} NMR (C6D6): δ 44.6 (s) ppm. Anal. Calcd. for

C37H31AuN3PFe: C, 55.45; H, 3.90; N, 5.24. Found: C, 55.18; H, 3.63; N 5.18.

[(PCy3)Au(1-benzyl-4-(4-biphenyl)triazolato)] (21). In 2 mL of acetonitrile in a glove box was suspended [(PCy3)Au(4-biphenylethynyl)] (75 mg, 0.12 mmol) and to this suspension was added a 1 mL acetonitrile solution of 3 equiv (46 mg, 0.35 mmol) benzyl azide. [Cu(MeCN)4]PF6 (4.3 mg, 0.012 mmol) was added to this suspension, and the resultant mixture was stirred for 12 h. The solvent was removed under rotary evaporation. The residue was triturated with pentane. An off-white solid was collected via filtration. This solid was dissolved in a minimum amount of benzne, and filtered through celite. Layering pentane onto the benzene solution led to the isolation of white crystals. The crystals were collected, washed with pentane, and

1 dried under vacuum. Yield: 68 mg (75%). H NMR (C6D6): δ 8.97 (d, biphenyl, 2H, J

= 8.4 Hz), 7.70 (d, biphenyl, 2H, J = 8.4 Hz), 7.60 (d, biphenyl, 2H, J = 7.2 Hz), 7.24

(t, biphenyl, 2H, J = 7.6 Hz), 7.11-7.21 (m, 5H), 5.61 (s, 2H, CH2-benzyl), 0.91-1.70

31 1 (m, 33H, C6H11) ppm. P{ H} NMR (C6D6): δ 58.1 (s) ppm. UV-Vis (2-MeTHF): λ

-1 -1 (ε, M cm ) 305 (18126) nm. Anal. Calcd. for C39H49AuN3P: C, 59.46; H, 6.27; 5.33.

Found: C, 59.18; H, 6.55; N, 5.61.

123

[(PCy3)Au(1-benzyl-4-(1-naphthyl)triazolato)] (22). In 1 mL of acetonitrile in a glove box was suspended [(PCy3)Au(1-ethynylnaphthalene)] (54 mg, 0.086 mmol) and to this suspension was added a 0.5 mL acetonitrile solution of 3 equiv (34 mg.

0.26 mmol) benzyl azide. [Cu(MeCN)4]PF6 (3.2 mg, 0.0086 mmol) was added to this suspension, and the resultant mixture was stirred for 12 h. The acetonitrile was removed under rotary evaporation. The residue was triturated with pentane in an ice bath. A red solid was isolated via filtration. The solid was then dissolved in a minimum amount of benzene and filtered through celite. Pentane was layered on top of the benzene solution. After approximately 2 days, no crystal was formed. A needle was put on the septum sealing the crystallization vial. Red crystals precipitated after a day. The crystals were collected, washed with pentane and dried in the air. Yield: 25

1 mg (38%). H NMR (C6D6): δ 9.37 (d, 1H, J = 8.4 Hz), 8.32 (d, 1H, J = 7.2 Hz), 7.71

(t, 2H, J = 7.2 Hz), 7.39 (t, 1H, J = 7.6 Hz), 7.20-7.35 (m, 4H), 7.08 (t, 2H, J = 7.6

Hz), 6.99-7.05 (m, 1H), 5.67 (s, 2H, CH2-benzyl), 0.70-1.60 (m, 33H, C6H11) ppm.

31 1 P{ H} NMR (C6D6): δ 57.7 (s) ppm. Anal. Calcd. for C37H47AuN3P: C, 58.34; H,

6.22; N, 5.52. Found: C, 58.09; H, 6.51; N, 5.64.

[(PCy3)Au(1-benzyl-4-(2-naphthyl)triazolato)] (23). Benzyl azide (3 equiv, 33 mg, 0.25 mmol) and CuI (2.3 mg, 0.012 mmol) were mixed in 2 mL acetonitrile and stirred for about 5 min. (PCy3)Au(2-ethynylnaphthalene) (51 mg, 0.081 mmol) was suspended in another 2 mL acetonitrile and the suspension was added to the above solution. The resultant mixture was stirred under Ar for 12 h. The solvent was

124 removed under rotary evaporation. The residue was triturated with pentane in an ice bath. The resulting solid was filtered out and dissolved in a minimum amount of benzene, and filtered through celite. Pentene was layered on top of the benzene solution, and colorless crystals were isolated. The crystals were collected, washed

1 with pentane and dried under vacuum. Yield: 39 mg (63%). H NMR (C6D6): δ 9.31 (s,

2-naphthyl, 1H), 9.08 (d, 2-naphthyl, 1H, J = 1.6, 8.4 Hz), 7.84 (t, 2-naphthyl, 2H, J =

8.8 Hz), 7.70 (d, 2-naphthyl, 1H, J = 8.0 Hz), 6.97-7.32 (m, 7H), 5.67 (s, 2H,

31 1 CH2-benzyl), 0.94-1.80 (m, 33H, C6H11) ppm. P{ H} NMR (C6D6): δ 57.9 (s) ppm.

HR-MS (ES+): Calcd. m/z = 762.3246 (M+H)+; Found m/z = 762.3240. 31P{1H}

-1 -1 NMR (CDCl3): δ 37.8 (s) ppm. UV-Vis (2-MeTHF): λ (ε, M cm ) 285 (16000), 301

(16300), 345 (2700) nm. Anal. Calcd. for C37H47AuN3P: C, 58.34; H, 6.22; N, 5.52.

Found: C, 58.10; H, 6.50; N, 5.51.

[(PCy3)Au(1-benzyl-4-(9-phenanthryl)triazolato)] (24). Benzyl azide (40 mg,

0.10 mmol) and [Cu(MeCN)4]PF6 (3.7 mg, 0.010 mmol, 10 mol%) was mixed in 2 mL acetonitrile, and the solution was stirred for 5 min.

[(PCy3)Au(9-ethynylphenanthrene)] (68 mg, 0.10 mmol) was suspended in about 1 mL acetonitrile and added to the above solution. The resulting mixture was stirred under Ar for 12 h. The solvent was removed under rotary evaporation. The residue was triturated with pentane in an ice bath. The solid was filtered out and dissolved in a minimum amount of benzene and filtered through celite. Layering pentane on top of

125 the benzene solution led to the isolation of colorless crystals. The crystals were

1 washed with pentane and dried under vacuum. Yield: 31 mg (38%). H NMR (C6D6):

δ 9.33-9.40 (m, 1H, 9-phenanthryl), 8.50-8.60 (m, 2H, 9-phenanthryl), 8.47 (s, 1H,

9-phenanthryl), 7.75 (d, 1H, 9-phenanthryl, J = 5.6 Hz), 7.33-7.45 (m, 6H), 7.00-7.14

31 1 (m, 3H), 5.72 (s, 2H, CH2-benzyl), 0.80-1.80 (m, 33H, C6H11) ppm. P{ H} NMR

-1 -1 (C6D6): δ 57.6 (s) ppm. UV-Vis (2-MeTHF): λ (ε, M cm ) 263 (14430), 311 (9254) nm Anal. Calcd. for C41H49AuN3P: C, 60.66; H, 6.08; N, 5.17. Found: C, 60.48; H,

5.93; N, 5.17.

126

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130

Chapter 4. Two-Photon Absorbing Gold(I) Styryl Benzene and

Naphthalene Complexes

4.1. Introduction

Linear, centrosymmetric conjugated oligomers (arylenevinylenes), such as distyryl benzene and distyryl naphthalene, Scheme 4.1.1, are considered as building blocks for two-photon absorbing chromophores.1 These compounds are easily synthesized from commercially available starting materials. Shown in Scheme 4.1.2 is the most commonly used sequence to build these oligomers. Commercially available symmetric aromatic materials with two methyl substituents first undergo electrophilic bromination with N-bromosuccimide at the two methyl positions. The brominated methyl groups further undergo a Michealis Arbuzuv reaction with a trialkylphosphite, usually triethylphosphite, to form a phosphonate-stabilized carbanion. This carbanion is then condensed with an aryl aldehyde (Horner-Wadsworth-Emmons reaction) to form the oligomer.2 The electronic properties of the conjugation system can be conveniently tuned by using different dimethyl-substituted aromatic systems and aldehydes.

Judicious introduction of electron donor and acceptor groups into these molecules to increase the degree of intramolecular charge transfer can significantly enhance the two-photon absorption probability. Finding proper electron donors and acceptors has invited intensive research.2

131

Scheme 4.1.1. Examples of Linear Centrosymmetric Oligo(arylenevinylenes).

Scheme 4.1.2. Common Reaction Sequence to Build Distryryl Benzene Systems.

Dialkyl and diaryl amino groups are usually used as terminal donor groups.

They not only provide efficient electron donation to the conjugated π system, but also enhance the solubility of the whole system.1, 3, 4

A wide range of electron acceptors have also been designed.5, 6 One excellent example is three-coordinate boryl substituents, Scheme 4.1.3.7-10 These are highly electron-deficient groups. Boron provides a vacant pz-orbital and is a strong

π-acceptor capable of significant delocalization.11-13 Mesityl substitution at boron is usually applied to stabilize the substituent.14

132

Scheme 4.1.3. Strong π-Electron Acceptor, BMes2.

Three systems with boryl substituents have been designed.14 The boryl substituents are either placed at one terminal position of the molecular long axis in push-pull systems, or at both termini to form an A–π–A (acceptor–π–acceptor) system.

Lately designed systems put the boryl substituents at the lateral positions of the

π-conjugated framework to form a D–A–D (Donor–Acceptor–Donor) electronic pattern. These compounds have unique solid-state emission properties.7-10

Since two-photon absorption (TPA) enables the absorption of two photons with half of the energy of one photon absorption to reach the excited states, it brings benefits to photodynamic therapy (PDT).14 The longer-wavelength (near-IR) light required for two-photon excitation penetrates deeper into living tissues than visible light, thus treatment depth and targeting can be improved. In PDT, singlet molecular

1 oxygen (a Δg) is acknowledged as an important reactive intermediate which can induce photooxidative damage of tumor cells.15-17 Figure 4.1.1 is a Jablonski diagram showing the process of generation of singlet oxygen from both one-photon and two-photon absorptions.2

133

Figure. 4.1.1. Jablonski Diagram of Singlet Oxygen Generation in One and Two-Photon

Excitations.

To be a good two-photon absorbing PDT reagent, enhancing the quantum yields of singlet oxygen generation without compromising the TPA cross sections is necessary. Functional groups which can induce intersystem crossing (such as carbonyl groups and heavy atoms such as bromine and iodine) are usually introduced into the

TPA system, to populate the lowest triplet excited states. However, it has been found that molecular features that increase charge transfer, which facilitates TPA, contribute to a low singlet oxygen generation yield.2 To address this issue, introducing functional groups which can both induce intramolecular electron transfer and potentiate intersystem crossing would be a good alternative. Phosphinegold(I) fragments are qualified .

+ 18 Phosphinegold(I) cations, such as PCy3Au , isolobal with the proton, are similar to boron. They also provide an empty pz orbial which allows p-π conjugation with the conjugated system, and are considered as efficient electron acceptors.

Meanwhile, the heavy atom effect of gold is well-known. By attaching a phosphinegold(I) fragment to the periphery of a chromophore, intersystem crossing can be greatly enhanced. In some systems, triplet state emission is observable at room 134 temperature.19-22

+ In this chapter, PCy3Au fragments will be attached to selected positions of distyrylbenzene (DSB) and distyrylnaphthalene (DSN) systems to investigate their effects on the emission properties, TPA cross sections and the singlet oxygen generation efficiency. Two synthetic strategies will be employed. In the first synthetic route, the conjugated systems will first be constructed. Halide substituents will be properly put on the selected positions. Palladium(I)-catalyzed borylation reactions will then be carried out, and subsequent base-promoted auration reactions will produce the Au(I) substituted DSB systems. In the second synthetic route, an aldehyde involved in Horner-Wadsworth-Emmons (HWE) reactions will first be modified by

Au(I) fragments, and the Au(I) modified conjugated systems will then be generated.

Further functionalization of the Au(I) fragments will also be performed. Conjugated systems modified by PCy3AuC≡C and PCy3Au(triazole) will be synthesized. All compounds will be fully characterized using NMR, MS, and elemental analysis.

UV-vis and fluorescence spectra will be collected. When applicable, crystal structures will be also be collected. Two-photon absorption cross sections will be measured and compared, and the singlet oxygen generation efficiency will be recorded. The effect of position as well as the number of the Au(I) fragments on the TPA cross sections and singlet oxygen generation efficiency will be discussed.

135

4.2. Results and Discussion

Shown in Scheme 4.2.1 are the potential two-photon absorbing compounds synthesized in this chapter. These compounds include one mono-gold(I) complex 1, and 10 digold complexes, 2, 3, 5-12, and one tetragold complex, 4. In compounds 1, 2,

5, 6, 9 and 11, the PCy3Au fragment is directly attached to the aromatic ring. In compounds 3, 4, 7, 10 and 12, a C≡C bond is installed between the aromatic ring and the PCy3Au fragment. In compound 8, the PCy3Au fragment is attached to the

4-carbon on a triazole ring, which is connected to the aromatic ring at the 5-position.

R2 R2'

AuPCy3 2. R1 =PCy3Au, R2 = t-Bu

3. R1 =PCy3AuC C, R2 =t-Bu 9. R1' =H, R2' =PCy3Au R1 4. R1 = R2 =PCy3AuC C 10. R1' =H, R2' =PCy3AuC C R1' R1 5. R1 =H, R2 =PCy3Au R1' 11. R1' =Br, R2' =PCy3Au 6. R1 =Br, R2 =PCy3Au 1 12. R1' =Br, R2' =PCy3AuC C 7. R1 =Br, R2 =PCy3AuC C

8. R1 =Br, R2 =PCy3Au-triazole R2

R2' Scheme 4.2.1. Synthesized Two-Photon Absorbing Gold(I) Complexes.

Shown in Scheme 4.2.2 is the synthetic pathway for Compound 1. Six steps are involved. First of all, a phosphonium bromide salt was synthesized by refluxing a benzene solution of triphenylphosphine and 4-t-butylbenzylbromide (a). The phosphoinum bromide salt was then dissolved in THF, and cooled to -78 oC. To this solution, n-BuLi was added slowly, and the solution took on a tan color. To this solution was added a THF solution of 4-bromobenzaldehyde dropwisely, and the resulting mixture was allowed to stir overnight (b). After the completion of the 136 reaction, 2-propanol was used to quench excess n-BuLi, and an orange residue was collected by evaporation. Adding ethanol to this orange residue led to the isolation a white iridescent product. This product is a mixture of both the E and Z isomers of

1-(4-bromostyryl)-4-tert-butylbenzene (TbsBr). Converting all the products into the E isomer is achieved by refluxing their toluene solution with the assistance of a piece of

I2 crystal (c).

Br Br Ph3P Br CHO PPh3 Br + C6H6/Reflux/18 h n-BuLi/THF

(a) E Z Br (b)

AuPCy3 O O B Br O O BB PCy3AuBr O O (B2(pin)2)

Cs2CO3/2-propanol Pd(dba)2/PCy3/KOAc 1 o L Dioxane/80 C/overnight (e) 1 E (d)

Scheme 4.2.2. Synthetic Pathway for Compound 1.

The palladium(0)-catalyzed cross coupling of bis(pinacolato)diboron with the

E-TbsBr was then carried out to synthesize L1, which is purified using vacuum sublimation. The following base-promoted auration led to the successful synthesis of compound 1, which was isolated as a white powder.

137

Scheme 4.2.3. Synthetic Pathway for Compounds 2 and 5-8.

Shown in Scheme 4.2.3 is the detailed synthetic pathway for compounds 2 and

5-8. Basically, there are five steps involved in the synthesis of each compound. The commercially available 1,4-diethyl benzene with or without two Br substituents first underwent electrophilic bromination with N-bromosuccinimide in benzene under reflux with a chain initiator, ABCN (I). The isolated products were then combined with triethyl phosphite, and refluxed for 6 h (II). This step is known as a

Michaelis-Arbuzov reaction, in which a trialkyl phosphite and an alkyl halide react to form a phosphonate. Upon cooling, the phosphonates precipitated out, and were collected via filtration. Additional products could be recovered upon the addition of hexanes. After the phosphonates were collected, the Horner-Wadsworth-Emmons reactions were carried out to produce the distyryl benzene skeletons, L’ (III). An orange color was visible upon refluxing the THF solution of the phosphonates and 138 aldehydes. The products were isolated by adding water to the suspension in THF, and collected via filtration. Compounds 5, 6 and 7 were directly synthesized in this step with 4-(PCy3Au)benzylaldehye or 4-(PCy3AuC≡C)benzylaldehyde as the starting materials. Combining compound 7 with azidotrimethylsilane in methanol led to the generation of the triazole, compound 8. Compound 2 was synthesized by base-promoted auration with L2, which was synthesized from the Pd(0)-catalyzed borylation reaction (IV).

Scheme 4.2.4. Synthetic Pathway for Compounds 3 and 4.

Compounds 3 and 4 were synthesized through the pathway shown in Scheme

4.2.4. Sonogashira coupling of L1 or L3 with trimethylsilylacetylene under the catalysis of Pd/Cu (VII, VII’) was used to attach a triple bond at the positions of the original Br substituents. These compounds were then desilylated with K2CO3 to afford the tetraethynyl distyryl benzene (VIII). Compounds 3 and 4 were synthesized following the procedures in the synthesis of phosphine gold(I) alkynyls as described in Chapter 3.

Attempts to synthesize the triazolato complexes from compound 3 were not successful, potentially due to the steric hindrance. 139

Scheme 4.2.5. Synthetic Pathway for Compounds 9-12.

The corresponding gold(I) distyryl naphthalene complexes were synthesized in a similar way, shown in Scheme 4.2.5. Step I’-III’ hold the same mechanisms as step

I-III, only with different starting materials. The only step of concern is step f. In this

o step, 2,6-dimethylnaphthalene was first dissolved in CH2Cl2, and cooled to -10 C. Fe powder and a piece of I2 crystal were added to the solution, and the mixture was degassed. While bubbling Ar through the solution, Br2 dissolved in CH2Cl2 was added slowly. After all the Br2 solution was added, the reaction was kept under Ar, warmed up to room temperature and stirred overnight. Upon reaction completion, the Fe metal was removed, and the solution was diluted with more CH2Cl2, washed with saturated

Na2SO3 solution and water several times. Removing the CH2Cl2 under rotary evaporation led to the collection of a solid, which was carefully washed with a small amount of hexanes. Excess amount of hexanes will lead to the loss of products. The 140 product should be a white crystalline powder. Unidentified materials would be produced if the reaction was handled in the air. Further purification can be achieved

23 by crystallizing the product in CHCl3.

L1 and compound 1 are isolated as white powders. Compound 1 is soluble in benzene. Diffusing pentane into a saturated benzene solution of compound 1 led to the isolation of colorless crystals. L2-L3, L1’-L3’, compound 2, 3, 5-7, and 9-12 are isolated as yellow powders. L2’ and L3’ are barely soluble in dichloromethane or chloroform. L1’ has better solubility due to the presence of two t-butyl groups. t-butyl groups on the Bpin substituents make L2-L4 very soluble. The digold(I) complexes are only soluble in dichloromethane and chloroform. Yellow crystals of compound 2 were collected by diffusing ether into a saturated CH2Cl2 solution. Crystallization of the other compounds only led to the precipitating of yellow powders, which are analytical pure. The more conjugated compounds, 4 and 8, have darker colors.

Crystallization led to the formation of orange crystals.

All the gold(I) complexes bearing Br substituents are not as soluble as those complexes without Br. Direct auration using L4 to make a tetragold(I) complex with the PCy3Au fragments directly attached to the phenyl ring was not very successful.

Product formation could be seen in high-resolution MS, but it is very light-sensitive.

Further trials to make this compound were not attempted.

31 1 P{ H} diagnoses the formation of Au-Caromatic and Au-C≡C bonds. As shown in

Table 4.2.1, the 31P{1H} peaks resonate at the expected ranges upon Au-C bond formation. The incorporation of a C≡C bond between the PCy3Au fragment and the

141 distyryl benzene/naphthalene group increases the conjugation length of the organic skeleton, making the organic skeleton more electron-donating. As a result, the 31P{1H} peaks tend to experience a slight upfield shift when an additional alkynyl group is present between the Au(I) atom and the aromatic skeleton. The triazole groups in compound 8 are not in efficient conjugation with the distyryl benzene skeleton, making the organic system relatively more electron-withdrawing, as seen from the further downfield shift of the 31P{1H} peak. In 1H NMR, the coupling constants of the the doublet of doublets assigned to the hydrogens attached to the ethylene groups are all about 16.0 Hz, indicating a trans-geometry according to the Karplus equation. The only exception is compound 1. The doublet of doublets of the two ethylene protons are not distinguished from the other peaks. The NMR spectra of the synthesized compounds can be found in Appendix II.

31P{1H} (ppm) 31P{1H} (ppm) Compound Compound (CDCl3) (CDCl3) 1a 57.5 3b 56.8 2a 57.9 4b 56.8, 56.7 5a 57.9 7b 56.9 6a 57.6 10b 56.9 9a 57.8 12b 56.9 11a 57.8 8c 58.5

Table 4.2.1. 31P{1H} chemical shifts of the gold(I) styryl benzene and naphthalene complexes. a, compounds with direct Au-Caromatic bonds; b, compounds with Au-C≡C bonds; c, the gold-triazolate compound (Au-Ctriazole).

142

Figure 4.2.1. Crystal structures (100 K) of compounds 1 and 4. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon. The PCy3 groups in 4 are disordered. Co-crystallized solvent molecules are not shown for clarity.

Shown in Figure 4.2.1 are the crystal structures for compound 1 and 4. The

Au(I) centers acqure a linear, two-coordinate geometry. The steric bulky PCy3 groups exclude short Au–Au interactions. One independent molecule resides in the assymetric unit of the crystal structure of 1. In the asymmetric unit of 4, one half-molecule resides on a crystallographic inversion center. The PCy3 groups in 4 are disordered. Two dichloromethane molecules crystallized in the asymmetric unit of 4.

The trans geometry across the double bonds can be observed in the crystal structures, consistent with the 1H NMR data. The structural characterization of compound 4

143 shows a nonplanar arrangement of the terminal and the central phenyl rings. The dihedral angle between the two best-fit planes along the long and short axis is 14.05°,

Figure 4.2.2. This may be due to the steric interference from the PCy3Au fragments.

Figure 4.2.2. Crystal structure of 4 illustrating the dihedral angle between best fit-planes along the long and short axis.

As seen from Table 4.2.2, in compounds 1 the Au(I) directly binds the aromatic skeleton, the Au-C length is 2.060(6) Å. The two Au–Calkynyl lengths measured in compound 4 are 1.983 (13) and 2.001 (10) Å, shorter than the Au–Caromatic observed in compounds 1. The ∠C–Au–P angles range from 175.5(3) in one half molecule of compound 4 to 176.02(15) of compound 1, showing the coordination mode around

Au(I) is essentially linear.

144

Compound 1 4

Au–C 2.060(6) Au–P 2.3087(15) 2.261(3), 2.263(3)

Au–Calkynyl 1.983(13), 2.001(10) C≡C 1.172(15), 1.179(13)

∠C–Au–P 176.03(15) 175.5(3), 177.6(3) ∠Au–C≡C 174.6(10), 176.2(9) ∠ C–≡C–R 175.6(10), 178.7(13) a The atom in boldface type lies at the vertex of the angle.

Table 4.2.2. Selected Interatomic Distances (Å) and Interatomic Angles (°)a in Crystallographically Characterized Gold(I) Complexes, 1 and 4.

Crystals were also collected for compound 2. The structure was partially solved.

Au(I) again acquires a linear, two coordinate geometry. Its crystallography data can be found in Appendix I.

145

1.2 a 1 2 1.0 5 6 0.8

0.6

0.4

0.2

0.0 250 300 350 400 450 500 Wavelength (nm)

1.2 b 3 4 1.0 7 8 0.8

0.6

0.4

0.2

0.0 250 300 350 400 450 500 Wavelength (nm)

Figure 4.2.3. Normalized absorption of spectra of gold(I) complexes with direct and indirect Au–Caromatic bonds

All the gold(I) complexes intensively absorb UV light. Shown in Figure 4.2.2 are the normalized absorption spectra of the compounds with direct Au–Caromatic bonds

(1, 2, 5 and 6) and indirect Au–Caromatic bonds (3, 4, 7 and 8) in the styrylbenzene series. Their emission maxima are shown in Table 3. All these compounds have strong absorption in the UV region. As seen from Figure 4.3.3a, the monogold compound 1 absorbs at much shorter wavelengths than the other compounds. In the

146 digold compounds, when the PCy3Au fragments are directly attached to the phenyl rings, a strong absorption peak occurs around 380 nm. This peak has no tremendous change upon changing the attachment positions from the central phenyl ring to the terminal ones. The digold compound 2 with two gold(I) fragments attaching to the central phenyl ring has another higher energy absorption peak at ~300 nm. The absorption profiles of 5 and 6 are essentially the same, with 6 emitting at longer wavelengths with a more structured emission pattern (Table 4.2.3). As seen from

Figure 4.2.3b, 3 and 4 have similar absorption patterns, with one higher energy absorption at ~330 nm, and lower energy absorption at 400 nm. Both the absorption and emission of compound 4 experience obvious red shifts compared with compound

3. This red shift occurs with the expansion of the conjugation system by incorporating

C≡C bonds (3, 4, 7, 10, and 12). Compared with compound 6, compound 7 has another low intensity absorption peak at ~275 nm. The absorption at longer wavelength experiences about 10 nm red shift. Their emission patterns are similar.

The triazolate compound 8 has similar absorption profile with compound 7, with the shorter wavelength absorption blue shifting to 255 nm. It emits at a comparatively long wavelength, similar to the tetragold alkynyl compound 4. There is no dramatic change in both absorption and emission profiles when substituting the central phenyl ring with a naphthalene ring.

As seen from Figure 4.2.4, the color of the compounds changes upon structural change. The monogold compound 1 is colorless in the solution. Compounds 5, 2, 4 and 8 are arranged in an order of intensifying colors. Compound 4 and 8 are dark

147 orange in solid states. All these compounds are blue-light emitters. The blue emission of the tetragold alkynyl compound 4 interferes with the solution color, and a green color was seen, Figure 4.2.4. These colors can be clearly seen under UV light in the dark. Their emission quantum yields (shown in Table 3) change with the structural change. The molecules tend to have higher emission quantum yields when the gold fragments bind the ends of the conjugated system, as seen from the high quantum yields of compounds 5 and 9 in Table 4.2.3 and the bright blue emission of 5 in

Figure 4.2.4. The blue emission of compound 2 and 8 is barely seen, consistent with their relatively lower quantum yields. At high concentrations, the blue emission of 8 is concealed by the dark orange color of the solution. At lower concentrations, a green color can be observed as seen in compound 4. When dissolving these compounds in a mixture of dichloromethane and methanol, the emission colors maintained, showing negligible solvent effects on the luminescence.

Figure 4.2.4. Compounds 1, 5, 2, 4 and 8 arranged by the intensity of their colors in dichloromethane and their emission under UV irradiation.

148

The absorption and emission spectra of these compounds can be found in

Appendix III.

Compound λex(nm) Em (nm) φ 1 325 357, 374 0.0540 2 371 427 0.0255 3 371 427 0.0242 4 389 447, 468 0.1238 5* 373 389, 411 0.5737 6 375 403, 429, 455 0.0707 7 383 421, 448 0.0630 8 378 462 0.0102 9* 371 400, 412 0.9440 10 383 417, 435 0.0340 11 380 430, 454 0.0226 12 389 415, 440 0.1509

Table 4.2.3. Emission Maxima and Quantum Yields (Ex. 325 nm, Standard: Anthracene, φ = 0.27 in ethanol) of the Gold(I) Styryl Benzene and Naphthalene Complexes. Compounds 5 and 9 are highly emissive, and their quantum yields were calculated using 7-diethylamino-4-methylcoumarin (Ex: 325 nm, φ = 0.56 in ethanol) as the standard.

The fluorescence quenching effect of the heavy atom (Br) rationalizes the lower fluorescence quantum yield of compound 11 compared to compound 9. The quenching effect of gold seems to be more effective in the alkynyl system 7 than in a triazolate system 8. Adding an alkynyl spacer between the gold fragment and the conjugated skeleton decreases the fluorescence quantum yields, as seen from the comparison of 2 and 3, 6 and 7, 9 and 10, as well as 11 and 12. Compound 4 with four gold alkynyl fragments also has a high emission quantum yield.

149

4.3. Conclusions

In this chapter, 12 new potential two-photon absorbing gold(I) complexes were synthesized, including one monogold, 10 digold and one tetragold compounds. In the synthesis of these compounds, base-promoted auration, alkynylation and triazolation methods employed in the last two chapters, as well as Horner-Wadsworth-Emmons reactions were used. Different distyryl benzene and naphthalene ligand systems were designed, and gold(I) substituents are attached to different positions of the conjugated system, either directly, or with an alkynyl or triazolate spacer. In some systems, Br substituents are also present. All these compounds are centrosymmetric.

The successful synthesis of these compounds were verified by NMR, HR-MS and

X-ray crystallography. 31P{1H} NMR diagonoses the attachment of the gold fragments to the conjugation system. When the gold fragments are directly attached to the aromatic skeleton, 31P{1H} peaks resonate around 58 ppm. When an alkynyl spacer is present between the gold fragments and the aromatic system, the 31P{1H} peaks resonate around 56 ppm. In 1H NMR, the coupling constants of ~16.0 Hz of the doublet of doublets assigned to the protons of the ethylene spacers show that all these compounds are trans-isomers. Crystal structures show a linear geometry of the gold(I) centers. No short Au–Au interactions were observed.

With the conjugation length increasing, the color of the solid compounds intensifies. The monogold(I) compound is colorless, and the digold(I) complexes change from yellow to orange. The tetragold(I) compound is dark orange. With more

Br substituents, the solubility of the compounds decreases. All these complexes

150 absorb UV light strongly, and emit from 350-450 nm. These emissions are not quenchable by oxygen, and no triplet state emission was observed at room temperature. The absorption and emission profiles experience small changes when changing the substituents. Fluorescence quantum yields change upon structural change. The highest quantum yields were observed when attaching two gold fragements directly to the two ends of the conjugated system. When there is an alkynyl spacer between the gold fragments and the conjugated system, the quantum yield decreases. The heavy atom effect of gold(I) fragments and Br substituents has quenching effect on the fluorescence, showing their potential to promote intersystem crossing. This effect is less efficient in the triazolate system than in the alkynyl system.

TPA cross sections and singlet oxygen generation efficiency will be carried out in the future upon availability of the facilities.

151

4.4. Experimental

4.4.1. Reagents

All commercially available reagents were used as received without further purification. [(PCy3)Au(4-formylphenyl)] was synthesized based on a base-promoted

20 auration procedure as reported. PCy3AuBr and [(PCy3)Au(4-ethynyllphenyl)] were synthesized following literature procedures.21, 24

4.4.2. Instrumentation

NMR Spectroscopy. NMR spectra (1H, 13C{1H}, and 31P{1H}) were recorded on a Varian AS-400 spectrometer. Chemical shifts are reported in parts-per-million

1 13 1 31 1 relative to Si(CH3)4 ( H, C{ H}), or 85% aqueous H3PO4 ( P{ H}).

Optical Properties Characetrization. UV-vis spectra were collected on a Cary

500 spectrophotometer in degassed HPLC grade solvents. Fluorescence measurements were done with a Cary Eclipse Spectrophotometer at room temperature.

All the luminescence spectra were collected both in the air and after being purged with argon.

X-Ray Structure Determinations. Single crystal X-ray data were collected on a

Bruker AXS SMART APEX CCD diffractometer using monochromatic Mo Kα radiation with the omega scan technique. The unit cells were determined using

SMAR25 and SAINT+. Data collection for all crystals was conducted at 100 K 152

4.4.3. Synthesis of Ligands and Gold(I) Complexes

1,4-dibromo-2,5-bis(4-tert-butylstyryl)benzene (L1’)

1,4-dibromo-2,5-diethylphosphonatebenzene (3.0 g, 5.6 mmol) and

4-tert-butylbenzaldehyde (2.0 g, 12.3 mmol) were combined in 30 mL THF. The resulting solution was transferred into the glove box, and NaH (0.54 g, 13.4 mmol) was added. The resulting suspension was cycled out of the box and put under reflux for 3 h. After cooling to RT, ice was added to the reaction mixture and stirred vigorously to generate a fine yellow suspension. Vacuum filtration led to the isolation of a yellow powder, which was washed with several times with THF and water, and

1 dried under vacuum. Yield: 1.90 g 61%. H NMR(CDCl3): δ (ppm) 7.87 (s, 2H), 7.50

(d, 4H, J = 8.4 Hz), 7.42 (d, 4H, J = 8.4 Hz), 7.33 (d, 2H, J = 16.0 Hz), 7.04 (d, 2H, J

= 16.4 Hz), 1.34 (s, 18H).

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1,4-dibromo-2,5-bis(4-bromostyryl)benzene (L3’)

1,4-dibromo-2,5-diethylphosphonatebenzene (3.0 g, 5.6 mmol) and

4-bromo-benzaldehyde (2.3 g, 12.3 mmol) were combined in 30 mL THF. The resulting solution was transferred into the glove box, and NaH (0.54 g, 13.4 mmol) was added. The resulting suspension was cycled out of the box and put under reflux for 3 h. After cooling to RT, ice was added to the reaction mixture and stirred vigorously to generate a fine yellow suspension. Vacuum filtration led to the isolation of a yellow powder, which was washed with several times with THF and water, and dried under vacuum. This material is not very soluble in chloroform. Yield: 1.0 g,

1 57%. H NMR(CDCl3): δ (ppm) 7.68 (s, 2H), 7.28 (d, 4H, J = 15.6 Hz), 7.23 (d, 4H,

J = 8.4 Hz), 6.89 (d, 2H, J = 8.4 Hz), 6.42 (d, 2H, J = 16.0 Hz).

These materials were pure by NMR and used without further purification.

1-Bpin-4-(4-tert-butylstyryl)benzene (L1)

Pd(dba)2 (3 mol%, 0.0096 g, 0.017 mmol) and PCy3 (7.2 mol%, 0.0112 g, 0.040 mmol) were combined in 5 mL degassed 1,4-dioxane in the glove box, and stirred for 30 min.

To this solution was added 1-bromo-4-(4-tert-butylstyryl)benzene (0.1750 g, 0.555 mmol), bis(pinacolato)diboron (B2pin, 0.1551 g, 0.610 mmol) and KOAc (0.0081 g,

0.834 mmol). The resulting mixture was transferred out of the box and heated under

Ar in an 80 oC oil bath overnight. Solvent was removed under rotary evaporation.

Vacuum sublimation led to the isolation of white crystals as the pure product. Yield:

1 0.1277 g, 63%. H NMR(CDCl3): δ (ppm) 7.79 (d, 2H, J = 8.0 Hz), 7.51 (d, 2H, J =

154

8.0 Hz), 7.47 (d, 2H, J = 8.4 Hz), 7.39 (d, 2H, J = 8.4 Hz), 7.17 (d, 1H, J = 16.4 Hz),

7.08 (d, 1H, J = 16.4 Hz), 1.34 (d, 21H, J = 8 Hz). m.p. 183-184 oC. Anal. Calcd. for

C23H30BO2: C, 79.09; H, 8.66. Found: C, 79.33; H, 8.39. UV-vis (CH2Cl2): λ (ε) 324

4 -1 -1 nm (4.33 × 10 M cm ). Emission (CH2Cl2, ex. 324 nm): 373 nm.

1,4-bis(Bpin)-2,5-bis(4-tert-butylstyryl)benzene (L2)

Pd(dba)2 (6 mol%, 0.0173 g, 0.030 mmol) and PCy3 (14 mol%, 0.0202 g, 0.072 mmol) were combined in 5 mL degassed 1,4-dioxane in the glove box, and stirred for 30 min.

To this solution was added 1,4-dibromo-2,5-bis(4-tert-butylstyryl)benzene (0.2706 g,

0.490 mmol), bis(pinacolato)diboron (B2pin, 0.1912 g, 0.753 mmol) and KOAc

(0.1428 g, 1.47 mmol). The resulting mixture was transferred out of the box and heated under Ar in an 80 oC oil bath overnight. Solvent was removed under rotary evaporation. The resulting residue was dissolved in CH2Cl2 and washed with water twice. The CH2Cl2 layer was collected and dried over MgSO4. Solvent was then removed under rotary evaporation, leaving a yellow powder. The powder was then dissolved in a minimum amount of CH2Cl2, and methanol was added until turbidity was seen. The suspension was allowed to sit for further precipitation. Vacuum filtration led to the isolation of the product as a yellow powder. Yield: 0.1678 g, 53%.

1 H NMR(CDCl3): δ (ppm) 8.16 (s, 2H), 7.99 (d, 2H, J = 16.4 Hz), 7.50 (d, 2H, J =

8.0 Hz), 7.39 (d, 2H, J = 8.0 Hz), 7.12 (d, 2H, J = 16.4 Hz), 1.43 (s, 24H), 1.35 (s, 18

o 4 -1 -1 H). m.p. 294 C (decomp). UV-vis (CH2Cl2): λ (ε) 369 nm (2.58 × 10 M cm ).

Emission (CH2Cl2, ex. 369 nm): 410 nm, 430 nm.

155

1,4-bis(4-Bpin-styryl)benzene (L3)

Pd(dba)2 (6 mol%, 0.0120 g, 0.021 mmol) and PCy3 (14 mol%, 0.0143 g, 0.051 mmol) were combined in 5 mL degassed 1,4-dioxane in the glove box, and stirred for 30 min.

To this solution was added 1,4-bis(4-bromostyryl)benzene (0.1536 g, 0.350 mmol), bis(pinacolato)diboron (B2pin, 0.1950 g, 0.768 mmol) and KOAc (0.1017 g, 1.05 mmol). The resulting mixture was transferred out of the box and heated under Ar in an

80 oC oil bath overnight. Solvent was removed under rotary evaporation. The resulting residue was dissolved in CH2Cl2 and washed with water twice. The CH2Cl2 layer was collected and dried over MgSO4. Solvent was then removed under rotary evaporation, leaving a yellow powder. The powder was then dissolved in a minimum amount of CH2Cl2, and methanol was added until turbidity was seen. The suspension was allowed to sit for further precipitation. Vacuum filtration led to the isolation of

1 the product as a yellow powder. Yield: 0.1237 g, 53%. H NMR(CDCl3): δ (ppm) 7.80

(d, 4H, J = 8 Hz), 7.51-7.54 (m, 8H), 7.19 (d, 2H, J = 16.0 Hz), 7.13 (d, 2H, J = 16.0

o 4 Hz), 1.36 (s, 24H). m.p. 306 C (decomp). UV-vis (CH2Cl2): λ (ε) 368 nm (5.01 × 10

-1 -1 M cm ). Emission (CH2Cl2, ex. 369 nm): 403 nm, 427 nm.

1,4-bis(Bpin)-2,5-bis(4-Bpin-styryl)benzene (L4)

Pd(dba)2 (12mol%, 0.0143 g, 0.0249 mmol) and PCy3 (28 mol%, 0.0167 g, 0.060 mmol) were combined in 5 mL degassed 1,4-dioxane in the glove box, and stirred for

30 min. To this solution was added 1,4-dibromo-2,5-bis(4-bromostyryl)benzene

(0.1240 g, 0.207 mmol), bis(pinacolato)diboron (B2pin, 0.2317 g, 0.912 mmol) and

156

KOAc (0.1209 g, 1.24 mmol). The resulting mixture was transferred out of the box and heated under Ar in an 80 oC oil bath overnight. Solvent was removed under rotary evaporation. The resulting residue was dissolved in CH2Cl2 and washed with water twice. The CH2Cl2 layer was collected and dried over MgSO4. Solvent was then removed under rotary evaporation, leaving an orange powder. The powder was then dissolved in a minimum amount of CH2Cl2, and methanol was added until turbidity was seen. The suspension was allowed to sit for further precipitation. Vacuum filtration led to the isolation of the product as an orange crystalline material. Yield:

1 0.060 g, 36%. H NMR(CDCl3): δ (ppm) 8.17 (s, 2H), 8.11 (d, 2H, J = 16.0 Hz), 7.81

(d, 4H, J = 8.0 Hz), 7.56 (d, 4H, J = 8.0 Hz), 7.15 (d, 2H, J = 16.4 Hz), 1.41 (s, 24H),

o 4 1.36 (s, 24H). m.p. 294-296 C (decomp). UV-vis (CH2Cl2): λ (ε) 373 nm (3.81 × 10

-1 -1 M cm ). Emission (CH2Cl2, ex. 373 nm): 414 nm, 437 nm, 463 nm.

These materials were pure by NMR and used without further purification.

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene (1)

[(PCy3Au)Br] (0.0923 g, 0.166 mmol), 1-bpin-4-(4-tert-butylstyryl)benzene (0.0900 g,

0.25 mmol), Cs2CO3 (0.1619 g, 0.50 mmol) were suspended in 10 mL isopropyl alcohol and charged into a round bottom flask. After degassing, the reaction vessel was immersed in a 50 oC oil bath, and stirred under Ar for 24 h. After cooling, isopropyl alcohol was removed under rotary evaporation, and the remaining solid was extracted into 50 mL benzene and filtered through celite. The solution was put under a rotary evaporator and benzene was removed. The residue was triturated with pentane.

157

Vacuum filtration gave the product as a white powder. The white powder was then dissolved in a minimum amount of benzene and filtered through celite. Diffusing pentane into the concentrated benzene solution afforded the product as colorless

1 crystals. Yield: 0.1000 g, 85%. H NMR(C6D6): δ (ppm) 8.13-8.17 (m, 2H), 7.69 (d,

2H, J = 7.6 Hz), 7.40 (d, 2H, J = 8 Hz), 7.20-7.27 (m, 4H); 1.34-1.85 (m, 24H,

31 1 (C6H11)3), 1.24 (s, 9H, t-butyl), 1.00-1.05 (m, 9H, (C6H11)3). P{ H} NMR (C6D6): δ

(ppm) 57.5. HR-MS (ES+): Calcd. m/z = 713.3550 (M+H)+, Found m/z = 713.3632.

Anal. Calcd. for C36H52AuP: C, 60.67; H, 7.35. Found: C, 60.41; H, 7.31. UV-vis

(2-MeTHF): λ (ε) 288 nm (3.65 × 104 M-1cm-1), 330 nm (3.95 × 104 M-1cm-1)

Emission (2-MeTHF, ex. 325 nm): 357 nm, 374 nm.

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene (2)

[(PCy3Au)Br] (0.0794 g, 0.142 mmol), 1,4-dibpin-2,5-bis(4-tert-butylstyryl)benzene

(0.0506g, 0.076 mmol), Cs2CO3 (0.1022 g, 0.31 mmol) were suspended in 10 mL isopropyl alcohol and charged into a round bottom flask. Benzene (5 mL) was then added to promote dissolution of the starting materials. After degassing, the reaction vessel was immersed in a 45 oC oil bath, and stirred under Ar for 24 h. After cooling, the solvents were removed under rotary evaporation, and the remaining solid was extracted into 100 mL of dichloromethane and filtered through celite. The solution was put under a rotary evaporator and the solvent was removed. The residue was triturated with pentane. Vacuum filtration gave the product as a yellow powder. The yellow powder was then dissolved in a minimum amount of dichloromethane and

158 filtered through celite. Diffusing ether into the concentrated dichloromethane solution

1 afforded the product as yellow crystals. Yield: 0.0640 g, 67%. H NMR(CDCl3): δ

(ppm) 7.89-7.91 (m, 2H), 7.78 (d, 2H, J = 16.0 Hz), 7.44 (d, 4H, J = 8.4 Hz), 7.29 (d,

4H, J = 8.4 Hz), 7.14 (d, 2H, J = 16.0 Hz), 1.55-2.08 (m, 66H, 2(C6H11)3), 1.32 (s,

31 1 + 18H, t-butyl). P{ H} NMR (CDCl3): δ(ppm) 57.9. HR-MS (ES ): Calcd. m/z =

+ 1348.6587 (M+H) , Found m/z = 1348.6978. Anal. Calcd. for C66H98Au2P2: C, 58.83;

4 H, 7.33. Found: C, 58.72; H, 7.19. UV-vis (CH2Cl2): λ (ε) 297 nm (1.85 × 10

-1 -1 4 -1 -1 M cm ), 380 nm (3.13 × 10 M cm ). Emission (CH2Cl2 ex. 380 nm): 425 nm.

2,5-bis(4-tert-butylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene (3)

[(PCy3Au)Cl] (85.2 mg, 0.166 mmol) was suspendened in 5 mL MeOH. KOtBu (17.1 mg, 0.153 mmol) and 1,4-diethynyl-2,5-bis(4-tert-butylstyryl)benzene (36.4 mg,

0.082 mmol) were combined in another 5 mL methanol, and the mixture was then added to the suspension of PCy3AuCl. The resulting suspension was stirred at room temperature overnight. The solvent was removed via rotary evaporation. The residue was extracted with CH2Cl2 and filtered through a layer of celite. CH2Cl2 was then removed by rotary evaporation and the resulting solid was triturated with pentane.

Diffusing pentane into a saturated CHCl3 solution yielded a yellow powder, which was washed with pentane and dried under vacuum. Yield: 0.0681 g, 60 %. 1H

NMR(CDCl3): δ (ppm) 7.83 (s, 2H), 7.78 (d, 2H, J = 16.4 Hz), 7.51 (d, 4H, J = 8.4

Hz), 7.34 (d, 4H, J = 8.8 Hz), 7.14 (d, 2H, J = 16.4 Hz), 1.43-2.05 (m, 66H). 31P{H}

+ NMR (400 MHz, CDCl3) δ 56.8 (s). MS (ES+): Calcd. m/z=1395.6475 (M+Na );

159

Found, 1395.7225. Anal. Calcd. for C70H98Au2P2, Calc: C, 60.25; H, 7.08. Found: C,

4 -1 -1 59.97; H, 6.80. UV-vis (CH2Cl2): λ (ε) 324 nm (4.53× 10 M cm ), 371 nm (2.35×

4 -1 -1 10 M cm ). Emission (CH2Cl2 ex. 371 nm): 427 nm.

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene (4)

[(PCy3Au)Cl] (113.4 mg, 0.221 mmol) was suspendened in 5mL of methanol.

1,4-diethynyl-2,5-bis(4-ethynylstyryl)benzene (20.4 mg, 0.054 mmol) and KOtBu

(24.2 mg, 0.216 mmol) were combined in another 5 mL of MeOH, and the mixture was then added to the suspension of PCy3AuCl. The resulting suspension was stirred at room temperature overnight. The solvent was removed via rotary evaporation. The residue was extracted with CH2Cl2 and filtered through a layer of celite. The solvent was then removed by rotary evaporation and the resulting solid was triturated with pentane. Diffusion of pentane into a saturated CHCl3 solution yielded orange crystals.

The crystals were washed with pentane and dried under vacuum as the pure product.

1 Yield: 0.1193 g, 96 %. H NMR(CDCl3): δ (ppm) 7.81 (s, 2H), 7.76 (d, 2H, J = 16.4

Hz), 7.41-7.45 (m, 4H), 7.11 (d, 2H, J = 16.0 Hz), 7.14 (d, 2H, J = 16.4 Hz),

31 1.50-2.02 (m, 132H). P{H} NMR (400 MHz, CDCl3) δ 56.852 (s), 56.742 (s). MS

(MALD): Calcd. m/z=2284.03 (M); Found, 2284.7. Anal. Calcd. for C102H146Au4P4,

Calc: C, 53.64; H, 6.44. Found: C, 53.38; H, 6.19. UV-vis (CH2Cl2): λ (ε) 282 nm

(3.37× 104 M-1cm-1), 333 nm (6.94× 104 M-1cm-1), 389 nm (4.85× 104 M-1cm-1) .

Emission (CH2Cl2 ex. 389 nm): 447 nm, 468 nm.

160

1,4-bis(4-[(PCy3)Au]styryl)benzene (5)

[(PCy3Au)Br] (0.0743 g, 0.133 mmol), 1,4-bis(4-bpinstyryl)benzene (0.0392g, 0.071 mmol), Cs2CO3 (0.0956g, 0.29 mmol) were suspended in 10 mL isopropyl alcohol and charged into a round bottom flask. Benzene (5 mL) was then added to promote dissolution of the starting materials. After degassing, the reaction vessel was immersed in a 45 oC oil bath, and stirred under Ar for 24 h. After cooling, the solvents were removed under rotary evaporation, and the remaining solid was extracted into

100 mL of dichloromethane and filtered through celite. The solution was put under a rotary evaporator and the solvent was removed. The residue was triturated with pentane. Vacuum filtration gave the product as a yellow powder. The yellow powder was then dissolved in a minimum amount of dichloromethane and filtered through celite. Diffusing ether into the concentrated dichloromethane solution afforded the

1 product as yellow crystals. Yield: 0.050 g, 61%. H NMR(CDCl3): δ (ppm) 7.49-7.53

(m, 4H), 7.46 (s, 3H), 7.42 (d, 4H, J = 6.8 Hz), 7.37 (d, 1H, J = 0.8 Hz), 7.06 (dd, 2H,

31 1 J = 24.4, 16.8 Hz), 1.52-2.06 (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ (ppm)

57.9. HR-MS (ES+): Calcd. m/z = 1235.5439 (M+H)+, Found m/z = 1235.5647. Anal.

Calcd. for C58H82Au2P2: C, 56.40; H, 6.69. Found: C, 56.66; H, 6.59. UV-vis

4 -1 -1 (CH2Cl2): λ (ε) 373 nm (1.32 × 10 M cm ). Emission (CH2Cl2 ex. 373 nm): 389 nm,

411 nm.

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene (6)

[(PCy3)Au(4-formylphenyl)] (0.0890 g, 0.133 mmol) and

161

1,4-dibromo-2,5-diethylphosphonatebenzene (0.0410g, 0.076 mmol) were dissolved in 20 mL THF. The solution was degassed and cycled into a glove box. NaH (0.0040 g,

0.17 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The resulting yellow powder was then redissolved in methylene chloride and washed with water three times. The methylene chloride layer was collected and dried over MgSO4.

The solvent was then removed under rotary evaporation. A yellow powder was

1 collected after trituration with pentane. Yield: 0.050 g, 61%. H NMR(CDCl3): δ (ppm)

7.85 (s, 2H), 7.51-7.54 (m, 4H), 7.44 (d, 4H, J = 6.8 Hz), 7.29 (d, 2H, J = 16.0 Hz),

31 1 7.01 (d, 2H, J = 16.0 Hz), 1.52-2.07 (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ

(ppm) 57.6. HR-MS (ES+): Calcd. m/z = 1393.3512 (M+H)+, Found m/z =

4 -1 -1 1393.4550. UV-vis (CH2Cl2): λ (ε) 375 nm (2.51× 10 M cm ). Emission (CH2Cl2 ex.

375 nm): 403 nm, 429 nm, 455 nm.

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene (7)

[(PCy3)Au(4-ethynyllphenyl)] (0.1288 g, 0.212 mmol) and

1,4-dibromo-2,5-diethylphosphonatebenzene (0.0683g, 0.127 mmol) were dissolved in 20 mL THF. The solution was degassed and cycled into a glove box. NaH (0.0061 g,

0.255 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction

162 mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The dried powder was then redissolved in methylene chloride, and washed with water twice. The methylene chloride layer was collected and dried over MgSO4. The solvent was then removed under rotary evaporation. A yellow powder was collected

1 after trituration with pentane. Yield: 0.0837 g, 55%. H NMR(CDCl3): δ (ppm) 7.84 (s,

2H), 7.50 (d, 4H, J = 8.4 Hz), 7.42(d, 4H, J = 8.4 Hz), 7.32 (d, 2H, J = 16.0 Hz), 7.00

31 1 (d, 2H, J = 16.4 Hz), 1.52-2.07 (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ (ppm)

56.9. HR-MS (ES+): Calcd. m/z = 1441.3512 (M+H)+, Found m/z = 1441.3093. Anal.

Calcd. for C62H80Au2P2Br2: C, 51.68; H, 5.60. Found: C, 51.41; H, 5.50. UV-vis

4 -1 -1 4 -1 -1 (CH2Cl2): λ (ε) 279 nm (1.92× 10 M cm ), 383 nm (4.03× 10 M cm ). Emission

(CH2Cl2 ex. 383 nm): 421 nm, 448 nm.

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene (8)

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene (0.0456 g, 0.032 mmol) was dissolved in 10 mL dichloromethane. To this solution was added azidotrimethylsilane

(0.0157 g, 0.13 mmol) and 5 mL methanol. The resulting solution was degassed and stirred under Ar at RT vigorously. After stirring for about 10 min, a turbidity was seen.

This turbidity dissappeared upon further stirring. After 48 h, solvents were removed under rotary evaporation, yielding a yellow residue, which was triturated to to generate a yellow powder. Vapor diffusion of pentane into a saturated CHCl3 solution yielded an orange crystalline solid, which was collected, washed with pentane and

163

1 dried under vacuum. Yield: 0.0341 g, 50%. H NMR(CDCl3): δ (ppm) 11.54 (br s,

2H), 8.37 (d, 2H, J = 8.4 Hz), 7.83-7.92 (m, 2H), 7.52-7.60 (m, 6H), 7.37 (d, 8H, J =

31 1 16.0 Hz), 7.10 (d, 2H, J = 16.0 Hz), 1.56-2.20 (m, 66H, 2(C6H11)3). P{ H} NMR

(CDCl3): δ (ppm) 58.5. MS (MALD): Calcd. m/z=1527.06 (M); Found, 1527. Anal.

Calcd. for C62H82Au2P2Br2N6: C, 48.77; H, 5.41, N, 5.50. Found: C, 49.03; H, 5.15, N,

4 -1 -1 4 5.24. UV-vis (CH2Cl2): λ (ε) 255 nm (2.41× 10 M cm ), 260 nm (2.02× 10

-1 -1 4 -1 -1 M cm ), 378 nm (3.07× 10 M cm ). Emission (CH2Cl2 ex. 378 nm): 462 nm.

2,6-bis(4-[(PCy3)Au]styryl)naphthalene (9)

[(PCy3)Au(4-formylphenyl)] (0.1235 g, 0.212 mmol) and

2,6-diethylphosphonatenaphthalene (0.0540g, 0.126 mmol) were dissolved in 20 mL

THF. The solution was degassed and cycled into a glove box. NaH (0.0060 g, 0.252 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The resulting yellow powder was then redissolved in methylene chloride and washed with water three times. The methylene chloride layer was collected and dried over MgSO4. The solvent was then removed under rotary evaporation. A yellow powder was collected after trituration with pentane. Diffusing pentane into a concentrated CHCl3 solution yielded a powder, which was collected, washed with pentane and dried under vacuum.

1 Yield: 0.040 g, 29%. H NMR(CDCl3): δ (ppm) 7.76 (d, 4H, J = 10.4 Hz), 7.71 (d,

164

2H, J = 9.6 Hz), 7.52-7.55 (m, 4H), 7.47 (d, 4H, J = 8.0 Hz), 7.19 (s, 4H), 1.56-2.07

31 1 + (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ (ppm) 57.8. HR-MS (ES ): Calcd. m/z

+ = 1285.5457 (M+H) , Found m/z = 1285.6199. Anal. Calcd. for C62H84Au2P2: C,

4 57.94; H, 6.59. Found: C, 58.21; H, 6.62. UV-vis (CH2Cl2): λ (ε) 291 nm (3.04× 10

-1 -1 4 -1 -1 M cm ), 371 nm (6.00× 10 M cm ). Emission (CH2Cl2 ex. 371 nm): 400 nm, 412 nm.

2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene (10)

[(PCy3)Au(4-ethynyllphenyl)] (0.2030 g, 0.335 mmol) and

2,6-diethylphosphonatenaphthalene (0.0792g, 0.185 mmol) were dissolved in 20 mL

THF. The solution was degassed and cycled into a glove box. NaH (0.0089 g, 0.370 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The dried powder was then redissolved in methylene chloride, and washed with water twice.

The methylene chloride layer was collected and dried over MgSO4. The solvent was then removed under rotary evaporation. A yellow powder was collected after trituration with pentane. Diffusing pentane into a concentrated CHCl3 solution yielded a powder, which was collected, washed with pentane and dried under vacuum. Yield:

1 0.1032 g, 46%. H NMR(CDCl3): δ (ppm) 7.77-7.80 (m, 4H), 7.70 (d, 2H, J = 8.8

Hz), 7.49-7.52 (m, 4H), 7.43 (d, 2H, J = 8.4 Hz), 7.20 (d, 2H, J = 6.8 Hz), 1.50-2.03

165

31 1 (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ (ppm) 56.9. HR-MS (FT-ICR): Calcd.

+ m/z = 1333.54521 (M+H) , Found m/z = 1333.54638. UV-vis (CH2Cl2): λ (ε) 279

4 -1 -1 4 -1 -1 nm (1.92× 10 M cm ), 383 nm (4.03× 10 M cm ). Emission (CH2Cl2 ex. 383 nm):

421 nm, 448 nm.

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene (11)

[(PCy3)Au(4-formylphenyl)] (0.1879 g, 0.323 mmol) and

1,5-dibromo-2,6-diethylphosphonatenaphthalene (0.1135 g, 0.194 mmol) were dissolved in 20 mL THF. The solution was degassed and cycled into a glove box. NaH

(0.0093 g, 0.387 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The dried powder was then redissolved in methylene chloride, and washed with water twice. The methylene chloride layer was collected and dried over MgSO4.

The solvent was then removed under rotary evaporation. A yellow powder was collected after trituration with pentane. Diffusing pentane into a concentrated CHCl3 solution yielded a powder, which was collected, washed with pentane and dried under

1 vacuum. Yield: 0.1688 g, 72%. H NMR(CDCl3): δ (ppm) 8.30 (d, 2H, J = 8.8 Hz),

7.87 (d, 2H, J = 9.6 Hz), 7.71 (d, 2H, J = 16.0 Hz), 7.51-7.55 (m, 8H), 7.18 (d, 2H, J

31 1 = 16.0 Hz), 1.58-2.17 (m, 66H, 2(C6H11)3). P{ H} NMR (CDCl3): δ (ppm) 57.8.

HR-MS (FT-ICR): Calcd. m/z = 1443.36421 (M+H)+, Found m/z = 1443.36617.

166

3 -1 -1 3 -1 -1 UV-vis (CH2Cl2): λ (ε) 245 nm (7.40 × 10 M cm ), 300 nm (6.12 × 10 M cm ).

Emission (CH2Cl2 ex. 380 nm): 430 nm, 454 nm.

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene (12)

[(PCy3)Au(4-ethynyllphenyl)] (0.1538 g, 0.254 mmol) and

1,5-dibromo-2,6-diethylphosphonatenaphthalene (0.0935 g, 0.159 mmol) were dissolved in 20 mL THF. The solution was degassed and cycled into a glove box. NaH

(0.0077 g, 0.318 mmol) was then added to the solution. The flask was then cycled out of the box and put under reflux for 4 h. After cooling to RT, ice was added to the reaction mixture under vigorous stirring. The yellow precipitate generated was collected by vacuum filtration, washed with THF and water several times, and dried in the air. The dried powder was then redissolved in methylene chloride, and washed with water twice. The methylene chloride layer was collected and dried over MgSO4.

1 vacuum. Yield: 0.0860 g, 47%. H NMR(CDCl3): δ (ppm) 8.33 (d, 2H, J = 9.2 Hz),

7.85 (d, 2H, J = 9.2 Hz), 7.74 (d, 2H, J = 16.0 Hz), 7.51 (dd, 8H, J = 15.2 Hz, 8.8

31 1 Hz), 7.15 (d, 2H, J = 16.0 Hz), 1.50-2.02 (m, 66H, 2(C6H11)3). P{ H} NMR

+ (CDCl3): δ (ppm) 56.9. HR-MS (FT-ICR): Calcd. m/z = 1491.36522 (M+H) , Found

m/z = 1491.36621. Anal. Calcd. for C66H82Au2P2Br2: C, 53.16; H, 5.54. Found: C,

4 -1 -1 52.92; H, 5.42. UV-vis (CH2Cl2): λ (ε) 315 nm (3.18× 10 M cm ), 389 nm (4.53×

167

4 -1 -1 10 M cm ). Emission (CH2Cl2 ex. 389 nm): 415 nm, 440 nm.

168

4.5. References

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P. R.; Jorgensen, M. J. Org. Chem. 2005, 70, 7065-7079.

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11. Entwistle, C. D.; Marder, T. B. Angew Chem. Int. Ed. 2002, 41, 2927-2931.

12. Entwistle, C. D.; Marder, T. B. Chem. Mater. 2004, 16, 4574-4585.

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170

Chapter 5. Metalloazadipyrromethene Complexes for Solar Energy

Conversion and Oxygen Evolution

5.1. Introduction

The largest renewable, carbon-neutral energy resource is provided by the sun. In one hour, about 4.3×1020 J of solar enery shines on the earth. This is comparable to all of the energy consumed on the planet in a year (4.1×1020 J in 2001). To solve the energy problem in the future, solar energy inevitably becomes the answer. In 2006,

Lewis and Nocera summarized the challenges in solar energy recovery as “capture, conversion, and storage”.1 Designing molecules which can absorb sunlight and convert it into chemical fuels (storing the solar energy in chemical bonds) has invited tremendous research efforts.2

Chromophoric ligands with absorption bands in the near-ultraviolet region are considered to be light harvesters. Binding these ligands to metal centers which can support two-electron redox chemistry has generated organometallic complexes which can undergo photosensitized production of energy-rich molecules. Starting from 1976,

H. B. Gray and coworkers have been reporting hydrogen production by photo-irradiation of rhodium(I) 1,3-diisocyanopropane complexes in HCl solutions,3-6

Scheme 5.1.1. Two equivalents of H2 can be generated per rhodium(I) dimer. Nocera and coworkers designed mix-valance dirhodium complexes which undergo four-electron photochemistry to produce hydrogen halides,7, 8 Scheme 5.1.2. Catalytic production of H2 was achieved by exciting Rh2dfpma (dfpma =

171 difluoro(methylamino)phosphine) in nonaqueous solutions containing HCl or HBr,

Scheme 5.1.3.7

Scheme 5.1.1. Photogeneration of H2 from Rh(I) dimers.

Scheme 5.1.2. Four-Electron Photochemistry of Dirhodium Cores.

Scheme 5.1.3. Photocatalytic Generation of H2 from Rh2dfpma in nonaqueous solutions.

172

In the catalytic HX splitting processes, the overall efficiency for the H2 photocycle is limited by the halogen photoelimination. Designing transition metal complexes which can increase the quantum yield of M–X activation thus becomes important. Recently, photoelimination of energetic compounds has been achieved by using late transition metals.9-11 Two equivalents of Cl· were generated by exciting a

PtIII-AuII bimetallic compound.9 The Cl· radicals were trapped by

2,3-dimethyl-1,3-butadiene. Energy-rich Cl2 and Br2 were generated by LMCT excitation of Au(III) complexes.11

To increase the solar-energy conversion efficiency, increasing the molar absorptivities at short wavelengths provides one prospect. One convenient way to achieve this goal is using conjugated ligands which are UV chromophores.

Azadipyrromethene ligands are very promising in this aspect. Although they have been mostly exploited as red light absorbers, they also absorb ultraviolet light.12 They readily bind metal centers, and an allowed optical transition near 300 nm carries over to the metallocomplexes.13-15 The molar absorptivities exceed 40 000 M-1cm-1. These ligand-centered states have enough energy to drive photochemistry, including HX cleavage and water splitting. Shown in Figure 5.1.1 are readily available azadipyrromethene ligands.

173

Figure 5.1.1. Azadipyrromethene Ligands.

Figure 5.1.2. Solar Energy Conversion by M-Azadipyrromethene Complexes.

Binding the azadipyrromethene ligands with metal centers which support oxidative addition/reductive elimination sequences provides the prospect to convert solar energy into chemical bonding energy. Figure 5.1.2 shows a proposed example.

The azadipyrromethene ligands harvest the solar energy in the UV region, and induce the photoelemination of Br2 from the metal center. The reduced metal center is stabilized by a capping ligand when the photoelimination is carried out in solutions.

Br2 can be collected as the solar energy carrier when solid state photoelimination is carried out. 174

In this chapter, synthesis of Au(I)/Au(III) azadipyrromethene (ligands shown in

Figure 5.1.1) complexes will be attempted. The Au(I) complexes are intended as the reduced products of light-induced elimination reactions. The Au(III) complexes will be synthesized either from the oxidation of the Au(I) compounds or from Au(III) starting materials. Once synthesized, photo-induced elimination of halides will be attempted both in solutions with chemical traps and in solid state without trap. All the gold azadipyrromethene compounds will be fully characterized by NMR and elemental analysis. Their absorption and emission spectra will be collected. Crystal structures will be collected whenever applicable.

175

The most attractive and clean energy source to solve the energy problem could be hydrogen. Finding a sustainable hydrogen source has long been the desire of various scientific fields.16 In nature, plants use sunlight to rearrange the chemical bonds of water to generate oxygen and hydrogen equivalents. Oxidation of water to dioxygen is the terminal reaction of photosystem II (PSII), equation 1. This reaction

17 takes place at a polynuclear Ca-Mn4 complex.

+ - 2H2O → O2 + 4H + 4e (1)

This reaction involves the oxidation of water by 4H+ and 4e-, thus creating tremendous molecular complexity from a mechanistic perspective. Meanwhile, it is thermodynamically demanding with E° = 1.23 V (vs SHE) at pH = 0. Properly modeling this reaction may lead to the first step toward creating a clean renewable source to generate hydrogen. Great success in water oxidation has been achieved by using ruthenium bipyridine complexes.18-22 Attempts to optimize the water oxidation catalysis have led to many complexes with modified ligand systems. Extensive mechanistic studies have been carried out. A metal oxo with the form of [RuV≡O]3+ is usually proposed as the intermediate in oxygen evolution.22

It has been proposed that oxygen evolution in PSII involves either a high valent terminal oxo manganese species or the coupling of bridging oxos.23-27 Manganese complexes have been extensively studied as artificial oxygen-evolving complex (OEC)

III/III V models. A phenylene-bridged Mn2 porphyrin dimer forms a (Mn =O)2 dimer upon oxidation with m-chloroperbenzoic acid under basic conditions.28 Acidification of the

176

V III/III (Mn =O)2 dimer leads to the regeneration of Mn2 dimer accompanied by water oxidation, Scheme 5.1.4. A Mn4O4 cubane-like complex releases its bridging oxides as water upon reduction and as O2 upon photo-excitation in the gas phase, providing a potential functional model for the OEC requiring the combination of the two separate

29 II/II reactions into one catalytic cycle. A bis(carboxylate)-bridged Mn2 dimer catalyzes water oxidation by the formation of higher valent oxo-bridged dimers in situ with tert-butylhydrogen peroxide as the primary oxidant.30 Another manganese-based

31 III IV 3+ water oxidation catalyst, [(H2O)(terpy)Mn (μ-O)2Mn (terpy)(H2O)] produces O2

27, 32 27, 31 catalytically with oxone (2KHSO5·KHSO4·K2SO4) or NaOCl as primary oxidants.

The other known enzyme that evolves O2 is chlorite dismustase. Chlorite dismutases are bacterial heme enzymes that catalyze the reaction:

- - ClO2 → O2 + Cl

Toxic chlorite is transformed into innocuous chloride and molecular oxygen. It is proposed that chlorite oxidizes a ferric porphyrin by two electrons to a compound

I-type (oxo)iron(IV) radical cation. Nucleophilic attack of hypochlorite forms an

- 33-35 intermediate with O–O bond which fragments to O2, Cl , and the ferric porphyrin.

Scheme 5.1.4 shows the O2 evolution pathways from a Mn2-dimeric porphyrin complex28 and chlorite dismustase.35

177

Scheme 5.1.4. O2 evolution from a Mn2-prophyrin dimer and chlorite dismustase.

In 2008, Burgess and coworkers designed an azadipyrromethene ligand which can support four-coordinate geometry,36 Figure 5.1.3. This ligand provides a very good skeleton to build Mn and Fe complexes which can support catalytic oxygen evolution.

Figure 5.1.3. The Azadipyrromethene Molecule Supporting Four-Coordination Geometry.

Four-coordinate Zn(II) complex will be synthesized using the azadipyrromethene ligand shown in Figure 5.1.3 to define the structural and spectroscopic consequences of metal binding. A vanadyl complex will be synthesized to study the compatibility of the azadipyrromethene ligand with metal oxos. Lastly,

178

Mn(III) and Fe(III) azadipyrromethene complexes will be synthesized and reacted with oxygen-atom donors to generate their oxos which will then be reacted with H2O,

OH- or OCl- to generate oxygen.

The coordination geometry of these compounds will be confirmed using X-ray crystallography. Absorption and emission spectra will be collected when applicable to study the optical property change upon metal binding.

179

5.2. Results and Discussion

Part 1. Au(I)/Au(III) Azadipyrromethene Complexes

All the azadipyrromethene ligands were synthesized based on a modified method developed by O’Shea’s group in 2004, shown in Scheme 5.2.1.12 Chalcones which are not commercially available can be easily synthesized from aldol condensation of an acetophenone and an aldehyde. Mixing the starting materials with a base, typically

KOH in an alcohol/water mixture led to a precipitate as the product. Michael addition of nitromethane to the chalcones led to the isolation of the reaction intermediates

(Ia-Id). These intermediates are usually isolated as oil. Further purification by crystallization in methanol led to the isolation of white powders. Usually, the isolated oil was directly used for the next step. The azadipyrromethenes were synthesized by refluxing a high-boiling alcohol (1-butanol or isopropyl alcohol) solution of the intermediate and approximately 35 equivalent of ammonium acetate. Upon heating, the reaction mixture underwent a dramatic color change from colorless or yellow to dark blue. Refluxing for a day was sufficient to drive the reaction to completion.

Upon removing most of the solvent, the products precipitated out. The products were then isolated by vacuum filtration and purified by washing with ethanol and water

(La-Ld).

180

Scheme 5.2.1. Synthetic Scheme for Azadipyrromethenes, Brominated Azadipyrromethanes, and Gold(I) Azadipyrromethene Complexes.

To protect the two pyrrolic positions, the protons were usually substituted by

12 halides. Br-substitution has been reported by O’Shea’s group. Br2 was used.

However, bromination with Br2 was not successful in our synthesis. A NBS-directed bromination process was developed. The isolated azadipyrromethene complexes were mixed with two equivalents of N-bromosuccinimide (NBS) in dichloromethene. A dark precipitate, which formed quickly upon stirring, was shown to be the desired products (LaBr2-LdBr2). The excess starting materials and byproducts can be washed away by dicholormethane, and the products were isoalted as dark powders. LbBr2 has a green tint. These compounds are sparingly soluble in common organic solvents, and were directly used for the synthesis of gold(I) complexes.

To synthesize the gold(I) azadipyrromethene complexes, the ligands were first mixed with two equivalent of base, KOtBu or NaOtBu to deprotonate the amine.

Upon mixing with the base in THF, the solution quickly took on a turquoise color. 181

This deprotonation step rendered the previously insoluble starting materials soluble in

THF. This reaction mixture was degassed, and further stirred under argon for several hours to overnight. The gold(I) starting material, PMe2PhAuCl, was transferred into the reaction flask. The solution was again purged with argon, and the resulting mixture was stirred for 48 h. The turquoise color maintained. Upon reaction completion, the solvent was removed under vacuum in an oil bath below 50 °C. A metallic red residue was always left behind. This residue was redissolved in benzene, and the benzene solution was filtered through celite to remove the insoluble by-products. After removing benzene under vacuum at 50 °C, triturating the residue led to the isolation of metallic red powders as gold(I) azadipyrromethene complexes.

31P{1H} NMR diagnoses the formation of the Au-N bond. The 31P{1H} of free

PMe2Ph occurs at -46 ppm, and that of PMe2PhAuCl appears at 4.20 ppm. The electron withdrawing (AuCl) group induces a 50 ppm downfield shift. Collected in

Table 5.2.1 are the 31P{1H} chemical shifts of all the gold(I) azadipyrromethene complexes. Compared with PMe2PhAuCl, a clear upfield shift of 5-6 ppm can be observed. Substitution with Br makes the azadipyrromethene group more electron-rich, as seen from the further upfield shift in 31P{1H} of 1 and 5 compared to

2-4. The electronic effect of methoxy substituents is not obvious based on 31P{1H}

31 1 + NMR. 2, 3 and 4 have similar P{ H} chemical shifts. Upon binding to PMe2PhAu fragment, a 0.1-0.4 ppm downfield shift of the meta and ortho protons of the proximal azadipyrromethene phenyl substituents is observed. The doublet assigned to the methyl groups on PMe2Ph experiences a 0.1-0.3 ppm upfield shift. All the NMR

182 spectra can be found in Appendix II.

Compound 31P{1H}

(ppm, C6D6) 1 -1.60 2 -0.821 3 -0.851 4 -0.787 5 -1.809

Table 5.2.1. 31P{1H} Chemical Shifts of the Gold(I) Azadipyrromethene Complexes.

Figure 5.2.1. Crystal structures (100 K) of compound 1-4. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon.

183

Compounds 1-5 can be further purified by crystallization. Diffusing pentane into a benzene solution or layering pentane on top of a benzene solution led to the isolation of analytically pure materials. Compounds 1-4 crystallize as diffraction quality crystals. Crystals of compounds 1, 2 and 4 take on a metallic red color, and 3 has a green tint. A greenish powder was collected for 5 after crystallization.

Shown in Figure 5.2.1 are the crystal structures of compound 1-4. Ligands with different substituents are clear. The Br substituents on the pyrrolic carbon in compounds 2-4 are seen, further proving the success of the NBS-directed electrophilic bromination.

1 2 3 4 Au–N1 2.140(3) 2.119(2) 2.111(4) 2.113(2) 2.104(4) Au–N2 2.420(4) 2.490(2) 2.602(4) 2.560(2) 2.581(4) Au–P 2.2093(12) 2.2071(8) 2.2282(13) 2.2179(8) 2.2287(13) ∠N1–Au–P 155.05(9) 158.48(7) 167.95(11) 160.00(7) 166.29(12) ∠P-Au-N2 125.29(9) 121.57(6) 114.51(10) 117.44(6) 114.56(10) ∠N1–Au–N2 77.29(12) 79.78(8) 76.90(14) 82.44(8) 78.46(15) a The atom in boldface type lies at the vertex of the angle.

Table 5.2.2. Selected Interatomic Distances (Å) and Interatomic Angles (°)a in Crystallographically Characterized Gold(I) Azadipyrromethene Complexes.

Table 5.2.2 are the selected bond lengths and bond angles. ∠N1–Au–P angles are close to linear, ranging from 155.05(9)° in 1 to 167.95(11)° in one independent molecule in 3. ∠P-Au-N2 angles are much smaller. Au-N1 lengths are normal, 184 ranging from 2.104(4) Å in one independent molecule in 3 to 2.119(2) Å in 2. Au–N2 are much longer, ranging from 2.420(4) Å in 1 to 2.602(4) Å in one independent molecule in 3, showing the Au(I) center only weakly binds to N2. This bond is shown using dashed line in Figure 5.2.1. All these compounds can be considered having

“pseudo-trigonal” geometries, and N1–Au–P bonds are essentially linear, which is consistent with the preference for linear geometry of gold(I).

The absorption feature of the ligands carries over upon metalation. Shown in

Figure 5.2.2 are the absorption and emission spectra of Ld, compound 1 and compound 5. The higher energy absorption band remains the same upon metalation, and the lower-energy absorption band experiences a 10 nm blue shift. Upon excitation,

Ld has one emission peak at 373 nm and a broad peak around 770 nm. Both emissions are very weak. The similar emission pattern is also observed in the gold(I) complexes.

The higher energy emission peak appears at a longer wavelength, 385 nm, and strongly intensifies. The lower energy emission band appears around 700 nm, with very low intensity.

Shown in Table 5.2.3 are the absorption and emission maxima for all the gold(I) azadipyrromethene complexes. The higher energy absorption peaks occur at similar wavelengths. The lower energy absorption peaks change with different substituents.

The methoxy or Br groups on the proximal azadipyrromethene phenyl substituents lead to the red shift of the lower energy peak. The methoxy substituents also lead to the red shift of the higher-energy emission peak. When comparing compound 1 with compound 5, it can be seen that further substituting the two pyrrolic protons with Br

185 does not change the absorption profile much, but induces a 30 nm blue shift of the higher energy emission peak.

35 40000 317 nm L 620 nm d 373 nm Solvent: CH Cl 30 35000 2 2 C=7.84E-6 M Ex:317 nm 30000 25 Emission Intensity (a.u.) Intensity Emission

25000 770 nm 20 ) -1 20000 cm

-1 15 (M

ε 15000 10 10000

5 5000

0 0 300 400 500 600 700 800 900 Wavelength (nm)

70000 250 Compound 1 316 nm 385 nm Solvent: 2-MeTHF 60000 C=2.91 E-6 M 610 nm Ex: 316 nm 200

50000 Emission Intensity (a.u) Intensity Emission 150 40000 ) -1 cm -1 30000 100 (M ε

20000

50 10000 671 nm

0 0 300 400 500 600 700 800 Wavelength (nm)

8000 50 605 nm Compound 5 Solvent: 2-MeTHF C=2.39E-5 M Ex:315 nm 40 6000 Emission Intensity (a.u.)

) 355 nm -1 4000 315 nm cm -1 20 (M ε

2000 10

0 0 300 400 500 600 700 Wavelength (nm)

Figure 5.2.2. Absorption and Emission Spectra for Ld, compound 1 and compound 5 in 2-MeTHF.

186

Typically, the emission peaks around 700 nm are very weak. It is not observable in compound 2, 4 and 5. In compound 3, there is a new absorption peak appearing at 400 nm. An emission shoulder in compound 3 and 5 appears around 435-500 nm. The actual absorption and emission spectra of compounds 2-4 can be found in Appendix

III.

Compound Absorption Maxima (nm) Emission Maxima (nm) 1 316, 610 385, 671 2 309, 585 359 3 315, 400, 610 372, 435-500 (sh), 670 4 312, 595 372 5 315, 605 355, 435-500 (sh)

Table 5.2.3. Absorption and Emission Maxima of the Gold(I) Azadipyrromethene Complexes; 2-MeTHF was used as the solvent.

50000 1 2 40000 3 4 5

30000

20000 Emission Intensity (a.u.) Emission Intensity 10000

0 400 450 500 550 600 650 700 750 800 Wavelength (nm)

Figure 5.2.3. Steady state emission spectra collected at 77 K in 2-MeTHF.

187

Steady state emission spectra were collected for these gold(I) azadipyrromethene complexes in 2-MeTHF at 77 K. As shown in Figure 5.2.3, a new emission peak around 500 nm was observed upon UV light excitation. This peak is missing in the steady state emission of free ligand Ld. It’s then assigned as a triplet state emission corresponding to the absorption at ~315 nm and the singlet state emission at 355-385 nm. Meanwhile, at 77 K, the lower energy emission at ~670 nm gains intensity in compounds 1, 2, 3 and 5. This peak is still invisible in compound 4 at 77 K.

Various methods have been tried to synthesize Au(III) complexes. Shown in

Scheme 5.2.2 are the synthetic pathways using Au(III) starting materials. With or without the presence of a base, no reaction was observed when mixing azadipyrromethene ligands with AuCl3 or Au(OAc)3. Au(OAc)3 has very poor solubility in various solvents. It is sparingly soluble even under reflux. Reacting the azadipyrromethene ligands with HAuCl4·H2O led to the generation of a bright green solution. This green solution was treated with AgSbF6. The final product was isolated as a metallic reddish powder, which is a hexafluoroantimonate azadipyrromethene salt as evidenced by X-ray crystallography. Similar results were obtained when using

KAuBr4·2H2O as the starting material. A hydrobromide salt was collected as evidenced by X-ray crystallography (the inset image in Scheme 5.2.2). If strong bases are used in reactions 2 and 3, starting azadipyrromethene ligands would be isolated.

Reaction 4 is similar to the synthesis of Au(I) azadipyrromethene complexes.

PMe2PhAuBr3 was first prepared by reacting PMe2PhAuBr with Br2 at room temperature. The 31P{1H} peak occurring at 12.24 ppm as compared to the starting

188 material (7.16 ppm) diagnoses the successful formation of the product. However, upon adding PMe2PhAuBr3 to the solutions of deprotonated azadipyrromethenes, free ligands were regenerated.

Scheme 5.2.2. Synthetic Pathways for Au(III) Azadipyrromethene Complexes.

Experiments were also done by reacting the synthesized Au(I)

azadipyrromethene complexes with Br2. Show in Scheme 5.2.3 is the proposed reaction. Typically, purified LaBr2Au was first dissolved in CH2Cl2, and the solution was cooled in an acetone/dry ice bath. Excess Br2 was dissolved in CH2Cl2 and added to the LaBr2Au solution dropwisely. The solution took on a bright green color instantaneously. Upon stirring, the solution turned purple, which is assumed to be a free ligand by color. The solution was kept in darkness and stirred for three days. The solution turned back to the original LaBr2Au color. Removing solvent and triturating 189 the residue with pentane led to the isolation of a metallic purplish-red powder. 31P{1H}

NMR taken in benzene shows a peak at 11.26 ppm (in LaBr2Au, it occurs at -0.82 ppm) The doublet assigned to the six methyl protons occurs at 1.23 ppm, experiencing approximately 0.8 ppm downfield shift compared to the original LaBr2Au. The spectra

31 1 collected in CDCl3 show the P{ H} peak at 12.11 ppm, and the doublet at 2.44 ppm

(in PMe2PhAuBr3, these peaks occur at 12.24 ppm and 2.44 ppm, respectively). It is then concluded that upon reacting the LaBr2Au with liquid Br2, a hydrobromide salt and PMe2PhAuBr3 were generated.

Scheme 5.2.3. Reaction of LBr2Au(I) with Br2.

190

Part 2. Synthesis and Characterization of Zinc, Vanadyl, Manganese and Iron

Azadipyrromethene Complexes

LOH which can give four potential coordination sites was synthesized following the literature procedures,36 which are similar to the synthesis of all the other azadipyrromethenes. Boiling the suspension of the isolated dark powder in methanol is a very efficient purification method. The product is only slightly soluble in chlorinated solvents, but fairly soluble in acetone.

As shown in Scheme 5.2.4, to make the Zn(II) complex, Zn(OAc)2·H2O or

ZnPh2 was added to a THF solution of LOH. The solution turned green instantaneously.

The solvent was removed after the reaction mixture was stirred overnight. A dark red residue was left. Acetone was used to extract this red residue, and the solution was filtered through celite. Acetone was then removed under rotary evaporation. The dark red residue was triturated with pentane, and a metallic red powder was isolated by filtration. All the other metallocomplexes were synthesized in a similar way. The reaction mixture took on different colors depending upon the metal being ligated, green for vanadyl, red for manganese and black for iron. Adding base, typically diethylamine, was not necessary, but it can tremendously accelerate the reactions. The reactions for manganese and iron proceeded within hours as seen from the change in color. The reaction with VO(acac)2 was relatively sluggish. No obvious color change was observed upon overnight stirring. Diethylamine was added to accelerate the reaction. All the products have a metallic appearance and very dark color. The starting materials to make compounds 8 and 9 were Fe(II) and Mn(II) salts. The Fe(II) and 191

Mn(II) centers were oxidized into Fe(III) and Mn(III) in the reaction process.

Scheme 5.2.4. Synthesis of Zinc, Vanadyl, Manganese, and Iron Azadipyrromethene Complexes.

The Zn(II) complex was crystallized by layering pentane onto an acetone solution. VIVO, Fe(III) and Mn(III) complexes were crystallized by diffusing pentane or hexanes into a THF solution. The Zn(II), vanadyl and Mn(III) complexes crystallized as red crystals, the Fe(III) complex crystallized as black crystals. X-ray diffraction crystallography illustrated that three Zn(II) centers were chelated by two

LOH, with two Zn(II) centers coordinating to two N atoms and two O atoms from the same LOH, the third one was chelated to the four O atoms from two LOH molecules,

Figure 5.2.4. The two Zn(II) centers within the coordination sphere of two individual

LOH also axially coordinate to a water molecule, and an acetone molecule, respectively. The vanadyl compound is a monomer, with the V(IV) center coordinating to two N and two O atoms from the same azadipyrromethene molecule.

The V=O bond length is 1.618(2) Å, and that of the starting material is 1.584(2) Å.37 192

This bond length is within the range of observed V=O bond lengths in four-coordinate complexes.38 A protonated diethylamine molecule resides in the asymmetric unit to balance the charge. The Mn(III) and Fe(III) complexes are dimers, with each metal center residing in an octahedral sphere. The metal is at the center of the plane that is

defined by two N atoms and two O atoms from one LOH. Axially, the metals are coordinated to one O atom from the other LOH positioned underneath and the O atom from a THF molecule. The charge balance calculation confirmed the valence of the vanadium center to be 4 and that of the manganese and iron centers to be 3, illustrating the occurrence of oxidation in the reaction or the work-up process. These three compounds have paramagnetic metal centers with d1, d4 and d5 d electron configurations, respectively.

Figure 5.2.4. Crystal structures (100 K) of compounds 6-9. 50% probability ellipsoids are shown. Hydrogen atoms are omitted for clarity. Unlabelled atoms are carbon.

193

Shown in Figure 5.2.5 are the absorption and emission spectra of LOH and compound 6 collected in acetone. In compound 6, the absorption maxima occur at 345,

430 and 700 nm. When comparing these maxima with those exhibited in the free

ligand LOH, the two higher-energy absorption peaks are essentially the same, and the molar absorptivities increase by about 2500 M-1cm-1. The lower-energy peak experiences an 85 nm red shift, and the molar absorptivity decreases by 4700 M-1cm-1.

Three emission peaks which are mirror images of the three absorption bands can be observed at 383, 457 and 700 nm. The average Stokes shifts are about 32 nm. These

emission peaks are not observable for the free LOH.

615 nm 20000 L in Acetone OH C=1.25 E-5 M

15000 ) -1

-1 10000 (M ε

340 nm

5000 425 nm

0 300 400 500 600 700 800 Wavelength (nm)

18000 6: ZnL OH 140 700 nm 16000 Solvent: Acetone

C=2.44E-5 M 120 14000 Ex: 345 nm

100

12000 Emission Intensity (a.u.)

) 457 nm -1 80 10000 cm -1 345 nm (M 8000 60 ε 430 nm

6000 732 nm 40

4000 383 nm 20

2000 0 300 400 500 600 700 800 900 Wavelength (nm)

Figure 5.2.5. Absorption and Emission Spectra for LOH and Compound 6 in Acetone.

194

The strong absorption is also carried over by the vanadyl complex, Figure 5.2.6.

The absorption in the UV region gains intensity, and the absorptivity of the red absorption band decreases.

11000

720 nm 7: VOL 10000 335 nm OH Solvent: THF 9000 C = 5.50 E-5 M 8000

7000 450 nm )

-1 6000 cm -1 5000 (M ε 4000

3000

2000

1000

0 400 600 800 1000 Wavelength (nm)

Figure 5.2.6. Absorption Spectrum of VOLOH (7) in THF.

Shown in Figure 5.2.7 is the absorption spectra collected for manganese (8) complex. The higher energy absorption maxima around 330 nm are slightly

blue-shifted compared to the LOH and ZnLOH (6). The two lower energy absorption bands experience red shifts, appearing at 473 nm and 809 nm, with a 48 nm and 194 nm red shift, respectively. The lowest energy peak has higher molar extinction absorptivity. A small shoulder peak at 738 nm appears on the lowest energy peak. No emission was observed at room temperature.

195

35000 8: MnL OH 809 nm Solvent: THF 30000 335 nm C = 4.13E-6 M

25000

) 20000 -1 cm

-1 15000 (M

ε 473 nm 736 nm 10000

5000

0 400 600 800 1000 Wavelength (nm)

Figure 5.2.7. Absorption spectra of compounds 8.

The THF solution of MnLOH is red, and that of FeLOH is black. Upon standing, the solution changes from black into brown, indicating decomposition.

196

5.3. Conclusions

Five new phoshinegold(I) azadipyrromethene complexes were synthesized.

31P{1H} NMR identifies the product formation. Compared to the 31P{1H} of the phosphine gold starting materials, the final compounds experience 5-6 ppm upfield shifts, occuring in the negative range.

These compounds are air stable, and all take on a metallic color in the solid state. Their solutions take on a turquoise color which distinguish them from the starting ligands. Crytal structures were collected for four of them. The gold(I) centers have a pseudo-trigonal geometry, with one Au–N bond much longer than the other one. As a result, they are still considered as two-coordinate, essentially linear.

Attempts to make Au(III) azadipyrromethene complexes by reacting Au(III) starting materials with free ligands, as well as directly oxidizing the Au(I) complexes with liquid Br2 have not yielded any promising results.

Zinc, vanadyl, manganese and iron azadipyrromethene complexes were synthesized. All these compounds are characterized by X-ray crystallography. The zinc centers take on tetragonal or pseudo-square-pyramidal geometries, defining the coordination styles of the ligand. Absorption and emission spectra of the Zn complex confirms that the absorption profile of the ligand is carried over upon metal binding.

Weak emission which is absent in the free ligand was observed for this compound.

The vanadyl compound is a monomer, with a d1 V(IV) center. The intact structure of this compound confirms that the ligand can support metal oxos in tetragonal ligand fields. Manganese and iron complexes are dimers, with Mn(III) and Fe(III) in an 197 octahedral coordination sphere. Two THF solvent molecules act as the anxial ligands.

In the future, the synthesis of Au(III) complexes will continue to be pursued.

Once successfully made, photoelimination of halides will be conducted both in solutions and solid states. Solution experiments will be carried out to study the reaction mechanism, and the solid state experiments will be carried out as the solar energy storage reactions. The Mn(III) and Fe(III) will be oxidized with properly chosen oxygen-atom donors to generate their oxos. Oxygen evolution reactions will be conducted with these oxos compounds in water or basic solutions. Acid-base reaction of OH- with electrophilic terminal oxo complexes of manganese(V) and ferric azadipyrromethenes with chlorite salts will be carried out for oxygen evolution.

To further prevent oxidative decomposition of the ligand and the dimerization of the oxo complexes, sterically hindered electron-deficient azadipyrromethene systems will be synthesized and used in the future synthesis.

198

5.4. Experimental

5.4.1. Reagents

Unless otherwise specified, commercially available reagents were used as received without further purification. PMe2PhAuCl, PMe2PhAuBr were synthesized based on modified procedures from the literature.

5.4.2. Instrumentation

NMR Spectroscopy. NMR spectra (1H, 13C{1H}, and 31P{1H}) were recorded on a Varian AS-400 spectrometer. Chemical shifts are reported in parts-per-million

1 13 1 31 1 relative to Si(CH3)4 ( H, C{ H}), or 85% aqueous H3PO4 ( P{ H}).

Optical Properties Characterization. UV-vis spectra were collected on a Cary

500 spectrophotometer in degassed HPLC grade solvents. Fluorescence measurements were done with a Cary Eclipse Spectrophotometer at room temperatures. All the samples were purged with argon for at least 15 min before the luminescence measurement. Steady state emission spectra were recorded at room temperature on an automated Photon Technology International (PTI) QM 4 fluorimeter equipped with a 150-W Xe arc lamp and a Hamamatsu R928 photomultiplier tube. Excitation light was excluded with appropriate glass filters.

Sample solutions were added to a quartz EPR tube, freeze pump thaw degassed (4 cycles, 1 × 10–5 Torr) and flame sealed. Low temperature emission spectra were 199 recorded in rigid solvent glass at 77 K by immersion of the sealed EPR tubes into a liquid nitrogen-filled dewar.

X-Ray Structure Determinations. Single crystal X-ray data were collected on a

Bruker AXS SMART APEX CCD diffractometer using monochromatic Mo Kα radiation with the omega scan technique. The unit cells were determined using

SMART39 and SAINT+. Data collection for all crystals was conducted at 100 K

5.4.3. Synthesis of Ligands and Gold(I) azadipyrromethene Complexes

1,3-bis(4-bromophenyl)-4-nitrobutan-1-one (Id)

(E)-1,3-bis(4-bromophenyl)prop-2-en-1-one (8.67 g, 23.7 mmol), nitromethane (7.22 g, 0.118 mol), and diethylammine (15.35 g, 0.210 mol ) were combined in 250 mL methanol and heated to reflux for 24 h. The resultant solution was put under a rotary evaporator and solvents and volatile materials were removed. A brown oily solid was

1 isolated. Yield: 3.3 g, 33%. H (CDCl3) δ (ppm) 7.779-7.757 (m, 2H); 7.619-7.597 (m,

2H); 7.477-7.455 (m, 2H); 7.170-7.150 (m, 2H); 4.793 (dd, J = 12.8 Hz, 6.8 Hz),

4.657 (dd, J = 12.4 Hz, 8.0 Hz); 4.185 (quiet, J = 6.8 Hz); 3.422 (d, J = 6.8 Hz).

200

(0Z)-N-(3,5-bis(4-bromophenyl)-2H-pyrrol-2-ylidene)-3,5-bis(4-bromophenyl)-1

H-pyrrol-2-amine (Ld)

Id and ammonium acetate (30 g, 0.390 mol) were combined in 200 mL 1-butanol and heated to reflux for 24 h. The solvent was stripped off and a dark residue was isolated.

This residue was washed with hot methanol and vacuum filtration led to the isolation

1 of a black solid. Yield: 2.2048 g, 74%. H (CDCl3) δ (ppm) 7.876 (d, 4H, J = 8.8 Hz);

7.770 (d, 4H, J = 8.4 Hz); 7.678 (d, 4H, J = 8.4 Hz); 7.558 (d, 4H, J = 8.8 Hz); 7.519

(s, 2H).

LdAuPMe2Ph (1)

Ld (0.2186 g, 0.286 mmol) and NaOtBu (0.0550 g, 0.573 mmol) were combined in 10 mL dry THF. The mixture was degassed under Ar for 5 min, and allowed to stir at RT under Ar overnight. PMe2PhAuCl (0.1086 g, 0.286 mmol) was then transferred to the reaction mixture, and the resulting mixture was degassed again for 5 min, and allowed to stir at RT under Ar for 48 h. THF was removed under vacuum, leaving a metallic dark red residue. Benzene was added, and the solution was filtered through celite. The filtrate was put in a 40 oC oil bath, and benzene was removed under vacuum.

Trituration of the residue with pentane led to the isolation of a metallic dark red powder. This powder was then dissolved in benzene, and vapor diffusion of pentane into the benzene solution led to the isolation of dark red crystals. Yield: 0.1870 g,

31 1 1 58%. P{ H} (C6D6) δ (ppm), -1.605; H (C6D6) δ (ppm) 8.10-8.13 (m, 4H), 7.78 (dd,

8H, J = 8.4 Hz, 1.6 Hz), 7.42 (d, 4H, J = 8.4 Hz), 7.23 (d, 4H, J = 8.4 Hz), 7.12 (s,

201

2H), 6.80-7.00 (m, 5H), 0.53 (bs, 6H). Anal. Calcd. for C40H29AuBr4N3P: C, 43.71; H,

2.66; N, 3.82. Found: C, 43.83; H, 2.43; N, 3.63. UV-vis (2-MeTHF): λ (ε) 316 nm

(6.16 × 104 M-1cm-1), 610 nm (5.36 × 104 M-1cm-1); Emission (2-MeTHF, ex. 312 nm):

385 nm, 671 nm.

LaBr2-LdBr2

L (1 eq.) was dissolved in 20 mL dry CH2Cl2, N-bromosuccinimide (2.2 eq.) was added. The solution was degassed under Ar, and stirred vigorously under Ar at room temperature. After several minutes, a precipitate was generated. The reaction mixture was kept under stirring overnight. Vacuum filtration led to the isolation of a black solid. This solid was washed several times with CH2Cl2, and dried under vacuum.

Yield: LaBr2: 67%, LbBr2: 77%, LcBr2: 78%, LdBr2: 79%.

LaBr2AuPMe2Ph (2)

LaBr2 (0.0251 g, 0.04 mmol) and KOtBu (0.0093 g, 0.082 mmol) were mixed in 10 mL dry THF. The mixture was degassed under Ar for 5 min, and allowed to stir at RT under Ar overnight. PMe2PhAuCl (0.0130 g, 0.04 mmol) was then transferred to the reaction mixture, and the resulting mixture was degassed again for 5 min, and allowed to stir at RT under Ar for 48 h. THF was removed under vacuum, leaving a metallic dark red residue. Benzene was added, and the solution was filtered through celite. The filtrate was put in a 40 oC oil bath, and benzene was removed under vacuum.

Trituration of the residue with pentane led to the isolation of a metallic dark red

202 powder. This powder was then dissolved in benzene, and vapor diffusion of pentane into the benzene solution led to the isolation of dark red crystals. Yield: 0.0210 g,

31 1 1 54%. P{ H} (C6D6) δ (ppm), -0.821; H (C6D6) δ (ppm) 8.07-8.10 (m, 4H),

7.94-7.97 (m, 4H), 7.17-7.26 (m, 5H), 7.01-7.05 (m, 4H), 6.95-7.00 (m, 4H),

6.88-6.92 (m, 2H), 6.72-6.77 (m, 2H), 0.45 (d, 6H, J = 10.4 Hz). Anal. Calcd. for

C40H31AuBr2N3P: C, 51.03; H, 3.32; N, 4.46. Found: C, 51.30; H, 3.38; N, 4.20.

UV-vis (2-MeTHF): λ (ε) 309 nm (3.40 × 104 M-1cm-1), 585 nm (8.45 × 104 M-1cm-1);

Emission (2-MeTHF, ex. 309 nm): 359 nm.

LbBr2AuPMe2Ph (3)

LbBr2 (0.1084 g, 0.16 mmol) and KOtBu (0.0360 g, 0.32 mmol) were combined in 10 mL dry THF. The mixture was degassed under Ar for 5 min, and allowed to stir at RT under Ar overnight. PMe2PhAuCl (0.0500 g, 0.16 mmol) was then transferred to the reaction mixture, and the resulting mixture was degassed again for 5 min, and allowed to stir at RT under Ar for 48 h. THF was removed under vacuum, leaving a metallic dark red residue. Benzene was added, and the solution was filtered through celite. The filtrate was put in a 40 oC oil bath, and benzene was removed under vacuum.

31 1 1 39%. P{ H} (C6D6) δ (ppm), -0.851; H (C6D6) δ (ppm) 8.11-8.13 (m, 4H),

8.00-8.02 (m, 4H), 7.25-7.29 (m, 5H), 6.89-6.99 (m, 3H), 6.78-6.86 (m, 2H),

203

6.65-6.67 (m, 5H), 3.21 (s, 6h), 0.54 (d, 6H, J = 10.0 Hz). Anal. Calcd. for

C43H35AuBr2N3O2P: C, 50.37; H, 3.52; N, 4.20. Found: C, 51.10; H, 3.31; N, 4.18.

HR-MS: Calcd. m/z = 1002.05561 (M+H)+, Found m/z = 1002.05508. UV-vis

(2-MeTHF): λ (ε) 315 nm (3.06 × 104 M-1cm-1), 400 nm (1.04 × 104 M-1cm-1), 610 nm

(7.60 × 104 M-1cm-1); Emission (2-MeTHF, ex. 315 nm): 372 nm, 467 nm, 670 nm.

LcBr2AuPMe2Ph (4)

LcBr2 (0.0704 g, 0.11 mmol) and KOtBu (0.0240 g, 0.22 mmol) were combined in 10 mL dry THF. The mixture was degassed under Ar for 5 min, and allowed to stir at RT under Ar overnight. PMe2PhAuCl (0.0330 g, 0.11 mmol) was then transferred to the reaction mixture, and the resulting mixture was degassed again for 5 min, and allowed to stir at RT under Ar for 48 h. THF was removed under vacuum, leaving a metallic dark red residue. Benzene was added, and the solution was filtered through celite. The filtrate was put in a 40 oC oil bath, and benzene was removed under vacuum.

31 1 1 28%. P{ H} (C6D6) δ (ppm), -0.787; H (C6D6) δ (ppm) 8.10-8.13 (m, 4H),

7.94-7.96 (m, 4H), 7.03-7.07 (m, 5H), 6.95-7.00 (m, 3H), 6.89-6.92 (m, 2H),

6.83-6.85 (m, 5H), 3.38 (s, 6h), 0.49 (d, 6H, J = 10.4 Hz). Anal. Calcd. for

C43H35AuBr2N3O2P: C, 50.37; H, 3.52; N, 4.20. Found: C, 50.65; H, 3.27; N, 4.01.

UV-vis (2-MeTHF): λ (ε) 312 nm (8.6 × 103 M-1cm-1), 595 nm (5.47 × 104 M-1cm-1);

204

Emission (2-MeTHF, ex. 312 nm): 372 nm.

LdBr2AuPMe2Ph (5)

LdBr2 (0.1040 g, 0.11 mmol) and KOtBu (0.0240 g, 0.22 mmol) were combined in 10 mL dry THF. The mixture was degassed under Ar for 5 min, and allowed to stir at RT under Ar overnight. PMe2PhAuCl (0.0330 g, 0.11 mmol) was then transferred to the reaction mixture, and the resulting mixture was degassed again for 5 min, and allowed to stir at RT under Ar for 48 h. THF was removed under vacuum, leaving a metallic dark red residue. Benzene was added, and the solution was filtered through celite. The filtrate was put in a 40 oC oil bath, and benzene was removed under vacuum.

31 1 1 g, 47%. P{ H} (C6D6) δ (ppm), -1.809; H (C6D6) δ (ppm) 7.68-7.72 (m, 4H),

7.46-7.49 (m, 4H), 7.31-7.34 (m, 4H), 7.11-7.12 (m, 4H), 7.00-7.02 (m, 3H),

6.71-6.76 (m, 2H), 3.38 (s, 6h), 0.42 (d, 6H, J = 10.4 Hz). Anal. Calcd. for

C40H27AuBr6N3P: C, 38.22; H, 2.16; N, 3.34. Found: C, 38.15; H, 2.06; N, 3.14.

UV-vis (2-MeTHF): λ (ε) 315 nm (3.54 × 103 M-1cm-1), 605 nm (7.24 × 103 M-1cm-1);

Emission (2-MeTHF, ex. 312 nm): 355 nm, 467 nm.

ZnLOH (6)

Zn(OAc)2·2H2O (0.1130 g, 0.51 mmol) and LOH (0.1653 g, 0.34 mmol) were

205 dissolved in 20 mL THF. The mixture was stirred vigorously overnight. THF was then removed under rotavap. This residue was extracted with acetone, and filtered through celite. Removing acetone under rotavap yielded a shiny reddish residue. This residue was triturated with pentane. A metallic reddish powder was collected by filtration. The powder was then again dissolved in acetone, and filtered through celite. Layering pentane on top of the acetone solution led to the isolation of red crystals. Yield:

0.1856 g, 88%. Anal. Calcd. for C67H48N3O6Zn3: C, 65.46; H, 3.94; N, 6.84. Found: C,

65.57; H, 4.14; N, 6.58. UV-vis (acetone): λ (ε) 345 nm (8.00 × 103 M-1cm-1), 430 nm

(6.02 × 103 M-1cm-1), 700 nm (1.60 ×104 M-1cm-1); Emission (acetone, ex. 345 nm):

383 nm, 457 nm, 732 nm.

VOLOH (7)

VO(acac)2 (0.0285 g, 0.08 mmol) and LOH (0.0394 g, 0.08 mmol) were dissolved in

10 mL THF. The mixture was stirred vigorously overnight. The solution gradually turned dark green. THF was then removed under rotavap to yield a dark green residue.

This residue was triturated with pentane. A dark green powder was collected by filtration. The powder was then dissolved in THF, and filtered through celite.

Diffusing pentane or hexanes into the THF solution led to the isolation of dark green crystals. Yield: 0.1232 g, 71%. Anal. Calcd. for (C4H12N)C32H20N3O3V·C4H8O: C,

69.46; H, 5.83; N, 8.10. Found: C, 69.54; H, 5.80; N, 8.29. UV-vis (THF): λ (ε) 335 nm (9.47 × 103 M-1cm-1), 450 nm (6.62 × 103 M-1cm-1), 720 nm (9.73 × 103 M-1cm-1)

206

MnLOH (8)

Mn(OAc)2·4H2O (0.0583 g, 0.24 mmol) and LOH (0.1156 g, 0.24 mmol) were dissolved in 20 mL THF. The mixture was stirred vigorously overnight. The solution gradually turned dark red. THF was then removed under rotavap to yield a dark red residue. This residue was triturated with pentane. A metallic dark red powder was collected by filtration. The powder was then again dissolved in THF, and filtered through celite. Diffusing pentane or hexanes into the THF solution led to the isolation of red crystals. Yield: 0.1125 g, 80%. Anal. Calcd. for C72H56N6O6Mn2: C, 71.40; H,

4.66; N, 6.94. Found: C, 71.11; H, 4.75; N, 6.83. UV-vis (THF): λ (ε) 335 nm (2.80 ×

104 M-1cm-1), 473 nm (1.25 × 104 M-1cm-1), 736 nm (1.07 ×104 M-1cm-1), 809 nm

(2.96 ×104 M-1cm-1)

FeLOH (9)

Fe(OAc)2 (0.0420 g, 0.24 mmol) and LOH (0.1163 g, 0.24 mmol) were dissolved in 20 mL THF. The mixture was stirred vigorously overnight. THF was then removed under rotavap to yield a black residue. This residue was triturated with pentane. A metallic black powder was collected by filtration. The powder was then again dissolved in

THF, and filtered through celite. Diffusing pentane into the THF solution led to the isolation of black crystals. Yield: 0.1044 g, 74%. Anal. Calcd. for C72H56N6O6Fe2: C,

71.30; H, 4.65; N, 6.93. Found: C, 71.27; H, 4.43; N, 6.68. UV-vis (THF): λ (ε) 330 nm (8.13 × 103 M-1cm-1), 493 nm (6.33 × 103 M-1cm-1), 635 nm (6.00 ×103 M-1cm-1),

845 nm (2.92 ×103 M-1cm-1), 946 nm (3.74 ×103 M-1cm-1)

207

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15729-15735.

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5. Sigal, I. S.; Mann, K. R.; Gray, H. B. J. Am. Chem. Soc. 1980, 102,

7252-7256.

6. Rice, S. F.; Miskowski, V. M.; Gray, H. B. Inorg. Chem. 1988, 27, 4704-4708.

7. Heyduk, A. F.; Macintosh, A. M.; Nocera, D. G. J. Am. Chem. Soc. 1999, 121,

5023-5032.

8. Esswein, A. J.; Veige, A. S.; Nocera, D. G. J. Am. Chem. Soc. 2005, 127,

16641-16651.

9. Cook, T. R.; Esswein, A. J.; Nocera, D. G. J. Am. Chem. Soc. 2007, 129,

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10. Cook, T. R.; Surendranath, Y.; Nocera, D. G. J. Am. Chem. Soc. 2009, 131,

28-+.

11. Teets, T. S.; Nocera, D. G. J. Am. Chem. Soc. 2009, 131, 7411-7420.

12. Gorman, A.; Killoran, J.; O'Shea, C.; Kenna, T.; Gallagher, W. M.; O'Shea, D.

F. J. Am. Chem. Soc. 2004, 126, 10619-10631. 208

13. Teets, T. S.; Partyka, D. V.; Esswein, A. J.; Updegraff, J. B.; Zeller, M.; Hunter,

A. D.; Gray, T. G. Inorg. Chem. 2007, 46, 6218-6220.

14. Teets, T. S.; Partyka, D. V.; Updegraff, J. B.; Gray, T. G. Inorg. Chem. 2008, 47,

2338-2346.

15. Teets, T. S.; Updegraff, J. B.; Esswein, A. J.; Gray, T. G. Inorg. Chem. 2009,

48, 8134-8144.

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17. Romero, I.; Rodriguez, M.; Sens, C.; Mola, J.; Kollipara, M. R.; Francas, L.;

Mas-Marza, E.; Escriche, L.; Llobet, A. Inorg. Chem. 2008, 47, 1824-1834.

18. Chen, Z. F.; Concepcion, J. J.; Jurss, J. W.; Meyer, T. J. J. Am. Chem. Soc.

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211

Chapter 6. Thesis Summary and Future Directions

6.1. Thesis Summary

Part 1. Organogold(I) Chemistry

Organogold chemistry, including direct Au–Caromatic bond formation, and synthesis of phosphine/N-heterocyclic carbene gold alkynyls and triazaolates was described. Scheme 6.1.1 shows the general reactions used in the synthesis.1-3

Scheme 6.1.1. Synthesis of Organogold(I) Complexes.

The direct Au–Caromatic bond formation (1) was achieved from base-promoted auration between aromatic organic boronates and gold(I) starting materials with labile substituents, such as Br, OAc, and N3. Nine new gold(I) naphthyl complexes were synthesized, including three monogold and six digold compounds with C2h or C2v symmetry.2 Gold(I) alkynyls were synthesized by mixing gold(I) chlorides with organic terminal alkynes deprotonated by a strong base (2).1 These compounds were 212 synthesized as precursors for the following Cu(I)-catalyzed Huisgen 1,3-dipolar cycloadditions.3 11 new gold(I) alkynyls were generated and fully characterized.

Synthesis of gold(I) triazolates was achieved by mixing the gold(I) internal alkynyls with organic azides, typically benzyl azide4 with Cu(I) as the catalyst (3). 16 new compounds with various functional groups were isolated and fully characterized. A series of new gold(I)-substituted distyryl benzene/naphthalene compounds were synthesized using the combination of reactions 1-3. With the availability of gold(I)-substituted phenyl aldehydes from reactions 1 and 2, modified

Horner-Wadsworth-Emmons reactions were used to conveniently generate these conjugated oligomers. 12 new compounds with the electron-accepting gold(I) substituents at specifically chosen positions were synthesized.

The formation of the products was easily diagnosed by the 31P{1H} NMR for those bearing phosphine ligands, and 13C{1H} NMR for those bearing N-heterocyclic

31 1 13 1 carbene ligands. Upon Au–C bond formation, both the P{ H} peak and C{ H} peak of the carbene ligand experience a downfield shift. The 31P{1H} peaks of

PCy3Au(I)–Caromatic systems occur around 58 ppm, and those of PPh3Au(I)–Caromatic systems occur around 44 ppm. When the gold(I) fragments bind C≡C, a slightly upfield shift of ~ 1 ppm can be seen. These 31P{1H} chemical shifts are very diagnostic of Au–C bond formation.

The heavy atom effect of gold is clearly manifested in those compounds bearing polycyclic aromatic functional groups. Strong triplet-state emission appears in all the gold(I) naphthyl compounds, with millisecond lifetimes of luminescence at 77 K. In

213 some cases, both singlet and triplet state emissions can be seen. The dual emission patterns are also observed in all the gold(I) alkynyl and gold(I) triazolate compounds with polycyclic aromatic substituents. The heavy atom effect is efficient even with the alkynyl/triazolate bridge between the gold(I) substituent and the polycyclic aromatic skeleton. However, only strong singlet state emission was observed for the two-photon absorbing compounds at room temperature.

Gold(I) starting materials with three sets of ancillary ligands were used. The absorption and emission patterns as well as emission lifetimes experience no obvious change upon the ancillary ligand changing. The most obvious change is the solubility.

The compounds bearing N-heterocyclic carbene ligands tend to have much better solubility than those bearing phosphine ligands.

X-ray crystal structures were collected whenever possible. In each compound, the gold(I) center has a linear, two coordinate geometry. No short Au–Au distances5 were observed, probably because of the bulky substituents around the gold centers.

The 1,4-regioselectivy of the copper-catalyzed cycloaddition was also authenticated by X-ray crystallography.

214

Part 2. Metalloazadipyrromethene complexes

Metallozadipyrromethene complexes were designed and synthesized for solar energy conversion and oxygen evolution.6, 7 Scheme 6.1.2 shows the reactions involved in the synthesis and the prospective solar energy conversion and oxygen evolution pathways.

Scheme 6.1.2. Metalloazadipyrromethene Complexe for Solar Energy Conversion and Oxygen Evolution.

(1) Au(I) azadipyrromethene complexes were first synthesized. The two pyrrolic protons were first substituted by Br.8 The ligands were treated with a strong base to deprotonate the amine group. Stirring the mixture of the deprotonated azadipyrromethene ligands and the gold(I) chloride starting material, PMe2PhAuCl, led to the isolation of the phosphine gold(I) azadipyrromethene complexes. The formation of the products can be readily monitored by the change of the 31P{1H} peak compared to the starting material. X-ray crystallography analysis further verified the formation of the products. One Au–N bond is much longer than the other one, and the

Au(I) center can still be considered as having a two coordinate, nearly linear geometry. 215

Five new compounds were synthesized and fully characterized. The absorption profiles were carried over upon metalation. The synthesis of the Au(III) complexes was attempted by using gold(III) starting materials. However, no success was obtained. Treating the synthesized Au(I) azadipyrromethene complexes with Br2 led to the isolation of a hydrobromide salt and phosphine Au(III) bromide. Further experiments are still needed to synthesize the Au(III) azadipyrromethene complexes.

(2) LOH, which can provide four coordination points, was synthesized to make metallo-complexes which can support O2 evolution. Zn(II) complex was first synthesized to define the structural and spectroscopic consequences of metal binding.

X-ray crystallography result showed that three Zn(II) centers bind two azadipyrromethene ligands, with each Zn(II) acquiring a tetragonal or square pyramidal geometry with the support of solvent molecules. The absorption profile of the ligand carried over upon metalation. Emission which is not observable in the free ligand occurred in the Zn(II) complex. With the structural and spectroscopic features defined, VOLOH was synthesized. The intact structure illustrated that the ligand can withstand metal oxos. Fe(III) and Mn(III) complexes were then synthesized as the reduced form of oxygen-evolving complexes. These complexes will further react with oxygen-donor ligands to generate their oxos, which can undergo O2 evolution reactions.

216

6.2. Future Directions

The base-promoted auration reaction will be used to functionalize organic molecules with gold(I) substituents. However, phosphinegold(I) tends to bind the nitrogen on molecules with active amine groups, such as indole. To generate Au–C bonds in this situation, the nitrogen position should first be protected.

Other copper sources will be developed and used to study their catalytic activity on the Huisgen 1,3-dipolar cycloaddition of alkynes and azides. The research effort will focus on the ease of isolation. The designed synthetic protocol will be applied to attach gold(I) fragments to different substrates to design potential anti-cancer drugs.

Two-photon absorption cross sections of the gold(I) distryryl benzene and naphthalene complexes will be measured and compared. Optimal positions of gold(I) installation, the number of gold(I) fragments and the geometry of the compound will be determined based upon the results. Meanwhile, the singlet oxygen generation efficiency of these compounds will also be measured, and the results will be associated with the two-photon cross sections as well as the structures.

The synthesis of Au(III) azadipyrromethene complexes will continue to be exploited. Upon success, the photo-elimination of Br2 will be conducted with future available facilities. Chemical traps will be used in solutions to study the photo-elimination mechanisms. Solid-state photo-elimination will also be conducted.

Br2 will be stored as the solar energy carrier.

The Mn(III) and Fe(III) azadipyrromethene complexes will be reacted with 217 oxygen-donor species to generate their oxos. These oxos will be reacted with H2O,

OH- or OCl- to evolve oxygen. Isotopic labeling experiments will probe the origins of the oxygen atoms in the gaseous product. The oxygen evolution process will be evaluated kinetically. To further prevent oxidative decompositon of the ligand and the dimerization of the oxo complexes, sterically hindered electron-deficient azadipyrromethene systems will be synthesized and used in the future synthesis.

218

6.3. References

1. Gao, L.; Partyka, D. V.; Updegraff, J. B.; Deligonul, N.; Gray, T. G. Eur. J

Inorg. Chem. 2009, 2711-2719.

2. Gao, L.; Peay, M. A.; Partyka, D. V.; Updegraff, J. B.; Teets, T. S.; Esswein, A.

J.; Zeller, M.; Hunter, A. D.; Gray, T. G. Organometallics 2009, 28,

5669-5681.

3. Partyka, D. V.; Gao, L.; Teets, T. S.; Updegraff, J. B.; Deligonul, N.; Gray, T. G.

Organometallics 2009, 28, 6171-6182.

4. Meldal, M.; Tornoe, C. W. Chem. Rev. 2008, 108, 2952-3015.

5. Schneider, W.; Bauer, A.; Schmidbaur, H. Organometallics 1996, 15,

5445-5446.

6. Teets, T. S.; Nocera, D. G. J. Am. Chem. Soc. 2009, 131, 7411-7420.

7. Nocera, D. G. Inorg. Chem. 2009, 48, 10001-10017.

8. Gorman, A.; Killoran, J.; O'Shea, C.; Kenna, T.; Gallagher, W. M.; O'Shea, D.

F. J. Am. Chem. Soc. 2004, 126, 10619-10631.

219

Appendix I. Crystallographic Data of Synthesized New Compounds

1. X-Ray crystallographic data for PCy3Au-2-naphthyl

Table AI-1a. Crystallographic data for GL_09 Table AI-1b. Data collection

C28H40AuP Bruker SMART CCD area-detector

Mr = 604.54 diffractometer

Triclinic, Pī  scans

a = 9.093(3) Å Absorption correction: multi-scan

b = 10.851(4) Å Tmin = 0.4411, Tmax = 0.2700

c = 12.724(4) Å 14172 measured reflections

α = 83.910(4) º 5428 independent reflections

 = 78.774(3) º 5209 reflections with I > 2(I)

γ = 83.093(4) º Rint = 0.0231

3 V = 1218.0(7) Å  max = 27.38º

Z = 2 h = -11  11

-3 Dx = 1.648 Mg m k = -14  13

Mo K radiation l = -16  16

Cell parameters from 6334 reflections

 = 1.64±27.38º

 = 6.118 mm-1

T = 100 (2) K

Irregular, colorless

0.29  0.28  0.16 mm

220

Table AI-1c. Refinement Figure AI-1a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0200 wR(F2) = 0.0554

S = 1.050

5428 reflections

271 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0415P) + 0.0187P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.142

-3 max = 3.108 eÅ

-3 min = -1.403 eÅ

Table AI-1d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.038(3) C(1)-Au(1)-P(1) 177.04(7) Au(1)-P(1) 2.2922(9) C(11)-P(1)-C(17) 104.98(11) P(1)-C(11) 1.830(3) C(11)-P(1)-C(23) 108.02(11) P(1)-C(17) 1.842(2) C(17)-P(1)-C(23) 104.44(11) P(1)-C(23) 1.855(2) C(11)-P(1)-Au(1) 112.55(8) C(1)-C(10) 1.376(4) C(17)-P(1)-Au(1) 113.54(8) C(1)-C(2) 1.422(4) C(23)-P(1)-Au(1) 112.66(8) C(11)-C(12) 1.530(3) C(10)-C(1)-C(2) 115.9(2) C(11)-C(16) 1.531(3) C(10)-C(1)-Au(1) 124.1(2) C(17)-C(18) 1.528(3) C(2)-C(1)-Au(1) 119.95(18) C(17)-C(22) 1.530(3) C(12)-C(11)-C(16) 109.02(19) C(13)-C(14) 1.526(4) C(12)-C(11)-P(1) 110.97(17) C(13)-C(12) 1.527(4) C(16)-C(11)-P(1) 111.38(16) C(3)-C(2) 1.365(4) C(18)-C(17)-C(22) 110.8(2) C(3)-C(4) 1.411(3) C(18)-C(17)-P(1) 110.89(17) C(23)-C(24) 1.526(4) C(22)-C(17)-P(1) 114.44(16) C(23)-C(28) 1.531(3) C(14)-C(13)-C(12) 111.5(2)

221

C(22)-C(21) 1.530(3) C(2)-C(3)-C(4) 120.7(2) C(9)-C(4) 1.414(3) C(24)-C(23)-C(28) 110.0(2) C(9)-C(10) 1.415(4) C(24)-C(23)-P(1) 116.20(17) C(9)-C(8) 1.417(4) C(28)-C(23)-P(1) 112.10(17) C(4)-C(5) 1.409(4) C(17)-C(22)-C(21) 110.8(2) C(5)-C(6) 1.360(4) C(4)-C(9)-C(10) 119.0(2) C(19)-C(18) 1.517(4) C(4)-C(9)-C(8) 118.6(2) C(19)-C(20) 1.522(4) C(10)-C(9)-C(8) 122.4(2) C(16)-C(15) 1.523(3) C(5)-C(4)-C(3) 122.8(2) C(6)-C(7) 1.404(4) C(5)-C(4)-C(9) 119.0(2) C(28)-C(27) 1.530(4) C(3)-C(4)-C(9) 118.2(2) C(21)-C(20) 1.520(4) C(6)-C(5)-C(4) 121.0(3) C(7)-C(8) 1.359(4) C(1)-C(10)-C(9) 123.3(2) C(25)-C(26) 1.511(4) C(18)-C(19)-C(20) 111.8(2) C(25)-C(24) 1.529(3) C(15)-C(16)-C(11) 110.6(2) C(15)-C(14) 1.510(4) C(19)-C(18)-C(17) 111.4(2) C(27)-C(26) 1.514(4) C(5)-C(6)-C(7) 120.2(3) C(27)-C(28)-C(23) 109.9(2) C(20)-C(21)-C(22) 111.0(2) C(13)-C(12)-C(11) 110.7(2) C(21)-C(20)-C(19) 110.7(2) C(8)-C(7)-C(6) 120.4(3) C(26)-C(25)-C(24) 111.4(2) C(14)-C(15)-C(16) 111.0(2) C(23)-C(24)-C(25) 110.2(2) C(26)-C(27)-C(28) 111.2(2) C(7)-C(8)-C(9) 120.8(3) C(3)-C(2)-C(1) 122.9(2) C(25)-C(26)-C(27) 111.6(2) C(15)-C(14)-C(13) 111.3(2)

222

2. X-Ray crystallographic data for 2,6-Bis(PCy3Au)-naphthalene

Table AI-2a. Crystallographic data for Table AI-2b. Data collection

GL-12_08mz062

C46H72Au2P2·CH2Cl2 Bruker AXS SMART APEX CCD

Mr = 1165.84 diffractometer

Triclinic, Pī  scans

a = 9.901(2) Å Absorption correction: multi-scan

b = 14.031(3) Å Tmin = 0.394, Tmax = 0.596

c = 18.294(4) Å 23996 measured reflections

α = 94.149(3) º 11526 independent reflections

 = 101.681(3) º 9250 reflections with I > 2(I)

γ = 107.990(3) º Rint = 0.0309

3 V = 2342.2(9) Å  max = 28.28º

Z = 2 h = -13  13

-3 Dx = 1.653 Mg m k = -18 18

Mo K radiation l = -24  24

Cell parameters from 6978 reflections

 = 1.15±28.28 º

 = 6.469 mm-1

T = 100 (2) K

Plate, colorless

0.16  0.15  0.08 mm

223

Table AI-2c. Refinement Figure AI-2a. ORTEP plot of the title

compound. Ellipsoids are at the 50% probability

level. The labels of H atoms and solvent

molecules are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0383 wR(F2) = 0.0765

S = 1.083

11526 reflections

535 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0291P) + 4.9197P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.161

-3 max = 2.084 eÅ

-3 min = -0.994 eÅ

Table AI-2d. Selected geometric parameters (Å, º). Au1-C1 2.035(5) C1-Au1-P1 178.75(16) Au1-P1 2.2984(14) C24-Au2 P2 179.08(15) Au2-C24 2.044(5) C2-C1-C4 116.8(5) Au2-P2 2.2968(14) C2-C1-Au1 122.4(4) C1-C2 1.379(7) C4-C1-Au1 120.7(4) C1-C4 1.400(8) C1-C2-C3 123.2(5) C2-C3 1.429(7) C3-C3-C5 118.3(6) C3-C3 1.419(10) C3-C3-C2 118.5(6) C3-C5 1.420(7) C5-C3-C2 123.2(5) C4-C5 1.386(7) C5-C4-C1 122.8(5) C5-C3 1.420(7) C4-C5-C3 120.3(5) C6-C11 1.530(7) C11-C6-C7 110.4(4) C6-C7 1.541(7) C11-C6-P1 117.5(4) C6-P1 1.854(5) C7-C6-P1 110.0(4)

224

C7-C8 1.540(8) C8-C7-C6 110.5(5) C8-C9 1.525(8) . C9-C8-C7 111.6(5) C9-C10 1.540(8) C8-C9-C10 113.1(5) C10-C11 1.540(7) C11-C10-C9 110.8(5) C12-C13 1.540(7) C6-C11-C10 112.3(4) C12-C17 1.547(7) C13-C12-C17 110.4(4) C12-P1 1.849(5) C13-C12-P1 109.3(4) C13-C14 1.533(8) C17-C12-P1 109.4(3) C14-C15 1.518(8) C14-C13-C12 111.8(5) C15-C16 1.505(8) C15-C14-C13 112.1(5) C16-C17 1.527(8) C16-C15-C14 111.1(5) C18-C23 1.528(7) C15-C16-C17 112.0(5) C18-C19 1.536(7) C16-C17-C12 111.9(5) C18-P1 1.849(5) C23-C18-C19 111.0(4) C19-C20 1.528(7) C23-C18-P1 111.5(4) C20-C21 1.516(8) C19-C18-P1 115.6(4) C21-C22 1.523(8) C20-C19-C18 110.6(4) C22-C23 1.542(8) C21-C20-C19 112.0(5) C24-C25 1.368(7) C20-C21-C22 111.2(5) C24-C27 1.424(8) C21-C22-C23 111.1(5) C25-C26 1.419(7) C18-C23-C22 111.3(5) C26-C26 1.414(10) C25-C24-C27 117.1(5) C26-C28 1.421(7) C25-C24-Au2 123.7(4) C27-C28 1.375(8) C27-C24-Au2 119.2(4) C28-C26 1.421(7) C24-C25-C26 123.2(5) C29-C30 1.539(7) C26-C26-C25 119.2(6) C29-C34 1.541(8) C26-C26-C28 117.5(6) C29-P2 1.847(5) C25-C26-C28 123.3(5) C30-C31 1.530(8) C28-C27-C24 121.3(5) C31-C32 1.510(8) C27-C28-C26 121.6(5) C32-C33 1.521(8) C30-C29-C34 110.7(4) C33-C34 1.530(8) C30-C29-P2 109.5(4) C35-C40 1.533(8) C34-C29-P2 109.0(4) C35-C36 1.536(8) C31-C30-C29 111.9(5) C35-P2 1.852(5) C32-C31-C30 111.3(5) C36-C37 1.525(8) C31-C32-C33 111.2(5) C37-C38 1.505(9) C32-C33-C34 110.8(5) C38-C39 1.507(9) C33-C34-C29 112.6(5) C39-C40 1.534(8) C40-C35-C36 110.2(5) C41-C46 1.532(8) C40-C35-P2 111.6(4) C41-C42 1.541(8) C36-C35-P2 115.6(4) C41-P2 1.846(6) C37-C36-C35 109.8(5) C42-C43 1.520(8) C38-C37-C36 112.0(5) C43-C44 1.527(9) C37-C38-C39 111.2(5)

225

C44-C45 1.515(9) C38-C39-C40 112.6(5) C45-C46 1.569(8) C35-C40-C39 111.3(5) C47-Cl1 1.88(2) C46-C41-C42 109.7(5) C47-Cl2 1.891(19) C46-C41-P2 117.9(4) C48-Cl3 1.89(2) C42-C41-P2 110.0(4) C48-Cl4 1.90(2) C43-C42-C41 112.0(5) C49-Cl5 1.89(2) C42-C43-C44 111.3(5) C49-Cl6 1.89(2) C45-C44-C43 112.8(5) C44-C45-C46 110.2(5) C41-C46-C45 112.9(5) C18-P1-C12 108.4(2) C18-P1-C6 106.7(2) C12-P1-C6 106.9(2) C18-P1-Au1 114.70(17) C12-P1-Au1 108.76(17) C6-P1-Au1 111.07(17) C41-P2-C29 107.6(3) C41-P2-C35 106.8(3) C29-P2-C35 108.1(2) C41-P2-Au2 110.67(18) C29-P2-Au2 110.81(18) C35-P2-Au2 112.70(18) Cl1-C47-Cl2 98.4(12) Cl3-C48-Cl4 95.1(16)

226

3. X-Ray crystallographic data for 2,7-Bis(PCy3Au)-naphthalene

Table AI-3a. Crystallographic data for Table AI-3b. Data collection

GL-119_08mz300

C46H72Au2P2 Bruker AXS SMART APEX CCD

Mr = 1080.91 diffractometer

Orthorhombic, Cmc21  scans

a = 21.8915(17) Å Absorption correction: multi-scan

b = 21.9518(19) Å Tmin = 0.312, Tmax = 0.407

c = 17.8889(15) Å 23853 measured reflections

α = 90 º 8921 independent reflections

 = 90 º 7738 reflections with I > 2(I)

γ = 90 º Rint = 0.0458

3 V = 8596.6(12) Å  max = 28.28º

Z = 8 h = -24  29

-3 Dx = 1.670 Mg m k = -29 20

Mo K radiation l = -19  23

Cell parameters from 4052 reflections

 = 1.14±28.28 º

 = 6.923 mm-1

T = 100 (2) K

Block, colorless

0.20  0.17  0.13 mm

227

Table AI-3c. Refinement Figure AI-3a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent molecules are

omitted for clarity. Tricyclohexyl groups exhibit

disorders, which are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0383 wR(F2) = 0.0765

S = 1.083

11526 reflections

535 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0837P) + 113.8186P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.289

-3 max = 6.714 eÅ

-3 min = -1.747 eÅ

Table AI-3d. Selected geometric parameters (Å, º). Au1-C1 2.026(19) C1-Au1-P1 178.7(5) Au1-P1 2.303(4) C7-Au2-P2 176.0(6) Au2-C7 2.00(2) C31-Au3-P3 177.4(5) Au2-P2 2.276(5) C2-C1-C10 116.6(17) Au3-C31 2.050(12) C2-C1-Au1 122.7(14) Au3-P3 2.291(3) C10-C1-Au1 120.7(14) C1-C2 1.38(3) C3-C2-C1 124.1(18) C1-C10 1.41(2) C2-C3-C4 119.7(19) C2-C3 1.36(3) C9-C4-C3 118.4(17) C3-C4 1.42(3) C9-C4-C5 120.3(18) C4-C9 1.39(3) C3-C4-C5 121.2(19) C4-C5 1.46(3) C6-C5-C4 117(2) C5-C6 1.33(3) C5-C6-C7 126.4(18) C6-C7 1.39(3) C6-C7-C8 115.2(18) C7-C8 1.40(3) C6-C7-Au2 125.0(14)

228

C8-C9 1.44(2) C8-C7-Au2 119.7(15) C9-C10 1.41(2) C7-C8-C9 123.6(18) C11-C12 1.526(12) C4-C9-C10 120.2(16) C11-C12 1.526(12) C4-C9-C8 116.9(16) C11-P1 1.781(12) C10-C9-C8 122.9(16) C12-C13 1.52(2) C9-C10-C1 121.0(17) C13-C14 1.51(3) C12-C11-C12 110.9(17) C14-C13 1.51(3) C12-C11-P1 113.2(9) C15-C20 1.537(14) C12-C11-P1 113.2(9) C15-C16 1.557(14) C13-C12-C11 114.0(17) C15-P1 1.761(13) C14-C13-C12 108.0(17) C16-C17 1.52(3) C13-C14-C13 112(2) C17-C18 1.53(3) C20-C15-C16 106.0(18) C18-C19 1.52(3) C20-C15-P1 111.8(16) C19-C20 1.52(3) C16-C15-P1 114.7(15) C15B-C20B 1.523(14) C17-C16-C15 115.6(17) C15B-C16B 1.551(14) C16-C17-C18 113(2) C15B-P1 1.794(13) C19-C18-C17 112(2) C17B-C18B 1.54(3) C18-C19-C20 109(2) C18B-C19B 1.52(3) C19-C20-C15 112(2) C19B-C20B 1.52(3) C20B-C15B-C16B 108.3(18) C21-C22B 1.529(14) C20B-C15B-P1 121.9(16) C21-C22 1.535(14) C16B-C15B-P1 117.9(15) C21-P2 1.817(13) C17B-C16B-C15B 116.5(16) C22-C23 1.533(14) C16B-C17B-C18B 111(2) C23-C24 1.533(15) C19B-C18B-C17B 109(2) C24-C23B 1.532(15) C20B-C19B-C18B 108.2(19) C23B-C22B 1.527(14) C19B-C20B-C15B 114(2) C25-C30 1.534(14) C22B-C21-C22 112.1(17) C25-C26 1.535(14) C22B-C21-P2 111.1(16) C25-P2 1.785(14) C22-C21-P2 108.6(16) C26-C27 1.56(3) C23-C22-C21 109.0(19) C27-C28 1.53(3) C22-C23-C24 112(2) C28-C29 1.47(3) C23B-C24-C23 109(3) C29-C30 1.545(15) C22B-C23B-C24 113(2) C25B-C30B 1.516(14) C23B-C22B-C21 110.9(19) C25B-C26B 1.537(14) C30-C25-C26 109.8(18) C25B-P2 1.811(13) C30-C25-P2 114.4(13) C26B-C27B 1.57(3) C26-C25-P2 115.2(13) C27B-C28B 1.53(3) C25-C26-C27 114.4(18) C28B-C29B 1.47(3) C28-C27-C26 111(2) C29B-C30B 1.546(15) C29-C28-C27 114(2) C31-C36 1.37(2) C28-C29-C30 112(2) C31-C32 1.42(2) C25-C30-C29 114.8(19)

229

C32-C33 1.360(18) C30B-C25B-C26B 110.8(19) C33-C34 1.425(16) C30B-C25B-P2 107.0(13) C34-C35 1.37(2) C26B-C25B-P2 121.4(17) C34-C33 1.425(16) C25B-C26B-C27B 114.2(19) C35-C36 1.433(14) C28B-C27B-C26B 110(2) C35-C36 1.433(14) C29B-C28B-C27B 113(2) C37-C42 1.537(14) C28B-C29B-C30B 115.7(19) C37-C38 1.572(14) C25B-C30B-C29B 115.5(18) C37-P3 1.773(13) C36-C31-C32 117.5(11) C38-C39 1.55(3) C36-C31-Au3 119.1(10) C39-C40 1.52(3) C32-C31-Au3 123.3(10) C40-C41 1.50(3) C33-C32-C31 121.4(13) C41-C42 1.42(3) C32-C33-C34 121.0(13) C37B-C42B 1.504(14) C35-C34-C33 118.5(8) C37B-C38B 1.542(14) C35-C34-C33 118.5(8) C37B-P3 1.765(13) C33-C34-C33 123.0(17) C38B-C39B 1.54(3) C34-C35-C36 119.8(8) C39B-C40B 1.51(3) C34-C35-C36 119.8(8) C40B-C41B 1.49(3) C36-C35-C36 120.3(17) C41B-C42B 1.42(3) C31-C36-C35 121.7(12) C43-C48 1.534(13) C42-C37-C38 104.2(16) C43-C44 1.551(12) C42-C37-P3 123.4(16) C43-P3 1.820(11) C38-C37-P3 108.0(14) C44-C45 1.52(3) C39-C38-C37 117.1(16) C45-C46 1.58(3) C40-C39-C38 115(2) C46-C47 1.49(3) C41-C40-C39 111(2) C47-C48 1.53(2) C42-C41-C40 112(2) C49-C54 1.515(14) C41-C42-C37 118.6(19) C49-C50 1.540(13) C42B-C37B-C38B 116.1(17) C49-P3 1.795(11) C42B-C37B-P3 117.2(15) C50-C51 1.52(2) C38B-C37B-P3 123.5(14) C51-C52 1.50(3) C37B-C38B-C39B 116.3(15) C52-C53 1.49(3) C40B-C39B-C38B 115(2) C53-C54 1.57(3) C41B-C40B-C39B 114(2) P1-C15 1.761(13) C42B-C41B-C40B 113(2) P1-C15B 1.794(13) C41B-C42B-C37B 117(2) P2-C25 1.786(14) C48-C43-C44 106.3(12) P2-C25B 1.811(14) C48-C43-P3 111.5(10) P2-C21 1.818(13) C44-C43-P3 110.1(10) C45-C44-C43 114.4(14) C44-C45-C46 109.5(15) C47-C46-C45 110.0(15) C46-C47-C48 110.7(15) C43-C48-C47 114.0(12)

230

C54-C49-C50 112.9(14) C54-C49-P3 117.5(11) C50-C49-P3 117.2(10) C51-C50-C49 113.7(12) C52-C51-C50 116.1(15) C53-C52-C51 111(2) C52-C53-C54 107.5(19) C49-C54-C53 107.9(17) C15-P1-C15 90.5(16) C15-P1-C11 116.1(9) C15-P1-C11 116.1(9) C15-P1-C15B 104.3(13) C11-P1-C15B 106.4(8) C15-P1-C15B 104.3(13) C11-P1-C15B 106.4(8) C15B-P1-C15B 117.9(19) C15-P1-Au1 110.1(7) C15-P1-Au1 110.1(7) C11-P1-Au1 112.1(6) C15B-P1-Au1 107.0(8) C15B-P1-Au1 107.0(8) C25-P2-C25 88.9(17) C25-P2-C25B 109.5(14) C25-P2-C25B 109.5(14) C25B-P2-C25B 128.3(18) C25-P2-C21 109.5(11) C25-P2-C21 117.6(11) C25B-P2-C21 102.0(11) C25B-P2-C21 92.4(11) C25-P2-C21 117.6(11) C25-P2-C21 109.5(11) C25B-P2-C21 92.4(11) C25B-P2-C21 102.0(11) C25-P2-Au2 110.8(6) C25-P2-Au2 110.8(6) C25B-P2-Au2 108.6(8) C25B-P2-Au2 108.6(8) C21-P2-Au2 116.0(6) C21-P2-Au2 116.0(6) C37B-P3-C49 108.5(11) C37-P3-C49 102.1(9) C37B-P3-C43 106.5(8) C37-P3-C43 118.2(8) C49-P3-C43 107.4(6)

231

C37B-P3-Au3 111.3(7) C37-P3-Au3 105.4(7) C49-P3-Au3 109.6(5) C43-P3-Au3 113.3(5)

232

4. X-Ray crystallographic data for PPh3Au-2-naphthyl

Table AI-4a. Crystallographic data for Table AI-4b. Data collection

GL-67_08mz127_0m

C28H22AuP Bruker AXS SMART APEX CCD diffractometer

Mr = 586.40  scans

Monoclinic, P21 /c Absorption correction: multi-scan

a = 16.3882(16) Å Tmin = 0.441, Tmax = 0.575

b = 9.9979(10) Å 21106 measured reflections

c = 14.3672(14) Å 5339 independent reflections

α = 90 º 4928 reflections with I > 2(I)

 = 113.9690(10) º Rint = 0.0209

γ = 90 º  max = 28.28º

V = 2151.0(4) Å3 h = -21  21

Z = 4 k = -13 13

-3 Dx =1.811 Mg m l = -19  19

Mo K radiation

Cell parameters from 9883 reflections

 = 1.36±28.28 º

 = 6.926 mm-1

T = 100 (2) K

Block, colorless

0.19  0.16  0.08 mm

233

Table AI-4c. Refinement Figure AI-4a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0174 wR(F2) = 0.0174

S = 1.067

5339 reflections

271 parameters H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0168P) + 2.0535P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.089

-3 max = 1.195 eÅ

-3 min = -0.788 eÅ

Table AI-4d. Selected geometric parameters (Å, º). Au1-C1 2.043(2) C1-Au1-P1 178.12(7) Au1-P1 2.2941(6) C10-C1-C2 116.5(2) C1-C10 1.379(3) C10-C1-Au1 121.31(17) C1-C2 1.430(3) C2-C1-Au1 122.20(17) C2-C3 1.369(3) C3-C2-C1 122.4(2) C3-C4 1.415(3) C2-C3-C4 120.9(2) C4-C5 1.421(3) C3-C4-C5 123.3(2) C4-C9 1.422(3) C3-C4-C9 118.3(2) C5-C6 1.363(4) C5-C4-C9 118.4(2) C6-C7 1.406(4) C6-C5-C4 121.2(2) C7-C8 1.370(3) C5-C6-C7 120.2(2) C8-C9 1.416(3) C8-C7-C6 120.3(2) C9-C10 1.429(3) C7-C8-C9 120.8(2) C11-C16 1.387(3) C8-C9-C4 118.9(2) C11-C12 1.404(3) C8-C9-C10 122.2(2) C11-P1 1.817(2) C4-C9-C10 118.8(2) C12-C13 1.386(3) C1-C10-C9 122.9(2) C13-C14 1.381(4) C16-C11-C12 119.1(2)

234

C14-C15 1.389(4) C16-C11-P1 122.54(18) C15-C16 1.390(3) C12-C11-P1 118.34(17) C17-C22 1.397(3) C13-C12-C11 120.3(2) C17-C18 1.399(3) C14-C13-C12 120.0(2) C17-P1 1.818(2) C13-C14-C15 120.2(2) C18-C19 1.386(3) C14-C15-C16 120.0(2) C19-C20 1.392(3) C11-C16-C15 120.3(2) C20-C21 1.384(3) C22-C17-C18 119.2(2) C21-C22 1.392(3) C22-C17-P1 122.75(18) C23-C24 1.394(3) C18-C17-P1 118.01(17) C23-C28 1.398(3) C19-C18-C17 120.4(2) C23-P1 1.822(2) C18-C19-C20 119.9(2) C24-C25 1.392(3) C21-C20-C19 120.1(2) C25-C26 1.389(4) C20-C21-C22 120.2(2) C26-C27 1.390(4) C21-C22-C17 120.2(2) C27-C28 1.388(3) C24-C23-C28 119.3(2) C24-C23-P1 123.28(18) C28-C23-P1 117.41(17) C25-C24-C23 120.4(2) C26-C25-C24 120.3(2) C25-C26-C27 119.4(2) C8-C27-C26 120.8(2) C27-C28-C23 119.9(2) C11-P1-C17 106.26(10) C11-P1-C23 104.85(10) C17-P1-C23 104.14(10) C11-P1-Au1 116.78(8) C17-P1-Au1 111.18(7) C23-P1-Au1 112.62(8)

235

5. X-Ray crystallographic data for 2,6-Bis(PPh3Au)-naphthalene

Table AI-5a. Crystallographic data for MC041708 Table AI-5b. Data collection

C46H36Au2P2 Bruker AXS SMART APEX CCD

Mr = 1044.62 diffractometer

Monoclinic, P21 /n  scans

a = 7.9096(16) Å Absorption correction: multi-scan

b = 12.458(3) Å Tmin = 0.2619, Tmax = 0.7320

c = 18.519(4) Å 18684 measured reflections

α = 90 º 5339 independent reflections

 = 101.521(2) º 4928 reflections with I > 2(I)

γ = 90 º Rint = 0.0618

3 V = 1788.1(6) Å  max = 26.83º

Z = 2 h = -10  9

-3 Dx =1.811 Mg m k = -15 15

Mo K radiation l = -23  23

Cell parameters from 4873 reflections

 = 1.98±26.83 º

 = 8.319 mm-1

T = 100(2) K

Irregular, colorless

0.22  0.06  0.04 mm

236

Table AI-5c. Refinement Figure AI-5a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0315 wR(F2) = 0.0868

S = 0.798

3814 reflections

226 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0168P) + 2.0535P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.177

-3 max = 1.039 eÅ

-3 min = -1.907 eÅ

Table AI-5d . Selected geometric parameters (Å, º). Au1-C18 2.024(7) C18-Au1-P4 175.7(2) Au1-P4 2.2652(19) C1-P4-C7 105.5(3) P4-C1 1.789(7) C1-P4-C13 104.2(3) P4-C7 1.794(7) C7-P4-C13 105.2(3) P4-C13 1.807(7) C1-P4-Au1 117.8(2) C2-C3 1.367(10) C7-P4-Au1 113.0(2) C2-C1 1.379(10) C13-P4-Au1 110.2(3) C10-C11 1.376(11) C- C2-C1 120.9(7) C10-C9 1.381(11) C11-C10-C9 120.8(7) C11-C12 1.388(10) C10-C11-C12 119.9(7) C5-C6 1.372(11) C6-C5-C4 118.9(7) C5-C4 1.394(12) C12-C7-C8 119.8(7) C7-C12 1.375(10) C12-C7-P4 119.2(6) C7-C8 1.401(10) C8-C7-P4 121.0(5) C8-C9 1.375(11) C9-C8-C7 120.2(7) C1-C6 1.397(10) C2-C1-C6 118.1(7) C4-C3 1.354(10) C2-C1-P4 124.1(5)

237

C15-C23 1.372(12) C6-C1-P4 117.7(6) C15-C14 1.386(10) C5-C6-C1 121.0(7) C14-C13 1.386(10) C8-C9-C10 119.4(7) C13-C16 1.380(10) C7-C12-C11 119.9(7) C17-C16 1.343(11) C3-C4-C5 120.3(7) C17-C23 1.387(12) C4-C3-C2 120.7(8) C18-C19 1.362(10) C23-C15-C14 119.5(8) C18-C20 1.429(10) C15-C14-C13 120.6(7) C19-C22 1.403(10) C16-C13-C14 118.1(7) C22-C22 1.390(14) C16-C13-P4 125.3(6) C22-C21 1.396(10) C14-C13-P4 116.5(5) C22-C19 1.403(10) C16-C17-C23 120.2(7) C21-C20 1.347(11) C17-C16-C13 121.8(8) C19-C18-C20 116.7(6) C19-C18-Au1 121.2(5) C20-C18-Au1 122.1(5) C18-C19-C22 123.5(7) C22-C22-C21 118.5(8) C22-C22-C19 118.5(8) C21-C22-C19 123.0(7) C20-C21-C22 122.2(7) C21-C20-C18 120.6(7) C15-C23-C17 119.7(7)

238

6. X-Ray crystallographic data for 2,7-Bis(PPh3Au)-naphthalene

Table AI-6a. Crystallographic data for MC041708 Table AI-6b. Data collection

C46H36Au2P2·C6H6 Bruker AXS SMART APEX CCD

Mr = 1122.73 diffractometer

Triclinic, Pī  scans

a = 9.3178(8) Å Absorption correction: multi-scan

b = 13.9021(13) Å Tmin = 0.1207, Tmax = 0.2299

c = 17.961(2) Å 23831 measured reflections

α = 67.6530(10) º 9112 independent reflections

 = 67.6530(10) º 8423 reflections with I > 2(I)

γ = 75.5320(10) º Rint = 0.0224

3 V = 2073.1(4) Å  max = 27.30º

Z = 2 h = -11  11

-3 Dx = 1.799 Mg m k = -17 17

Mo K radiation l = -22  23

Cell parameters from 9980 reflections

 = 1.23±27.30 º

 = 7.182 mm-1

T = 100(2) K

Irregular, yellow

0.51  0.29  0.29 mm

239

Table AI-6c. Refinement Figure AI-6a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent molecules are

omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0196 wR(F2) = 0.0641

S = 1.154

9112 reflections

505 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0409P) + 2.1716P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.152

-3 max = 0.879 eÅ

-3 min = -1.388 eÅ

Table AI-6d. Selected geometric parameters (Å, º). Au(2)-C(5) 2.036(3) C(5)-Au(2)-P(2) 174.95(10) Au(2)-P(2) 2.2930(9) C(1)-Au(1)-P(1) 172.04(10) Au(1)-C(1) 2.051(4) C(29)-P(2)-C(35) 106.38(16) Au(1)-P(1) 2.2874(9) C(29)-P(2)-C(41) 106.03(15) P(2)-C(29) 1.811(3) C(35)-P(2)-C(41) 105.51(16) P(2)-C(35) 1.812(4) C(29)-P(2)-Au(2) 110.24(11) P(2)-C(41) 1.814(3) C(35)-P(2)-Au(2) 114.83(12) P(1)-C(11) 1.813(4) C(41)-P(2)-Au(2) 113.24(11) P(1)-C(17) 1.815(4) C(11)-P(1)-C(17) 104.45(16) P(1)-C(23) 1.816(3) C(11)-P(1)-C(23) 104.37(16) C(1)-C(2) 1.376(5) C(17)-P(1)-C(23) 105.24(16) C(1)-C(10) 1.417(5) C(11)-P(1)-Au(1) 119.71(12) C(3)-C(4) 1.411(5) C(17)-P(1)-Au(1) 112.85(12) C(3)-C(2) 1.417(5) C(23)-P(1)-Au(1) 109.02(11) C(3)-C(8) 1.425(5) C(2)-C(1)-C(10) 116.6(3) C(41)-C(42) 1.394(5) C(2)-C(1)-Au(1) 118.6(3) C(41)-C(46) 1.391(5) C(10)-C(1)-Au(1) 124.7(3)

240

C(17)-C(18) 1.390(5) C(4)-C(3)-C(2) 123.1(3) C(17)-C(22) 1.389(5) C(4)-C(3)-C(8) 118.4(3) C(12)-C(13) 1.385(5) C(2)-C(3)-C(8) 118.5(3) C(12)-C(11) 1.397(5) C(42)-C(41)-C(46) 119.2(3) C(9)-C(10) 1.362(5) C(42)-C(41)-P(2) 117.3(3) C(9)-C(8) 1.414(5) C(46)-C(41)-P(2) 123.5(3) C(8)-C(7) 1.406(5) C(18)-C(17)-C(22) 119.1(3) C(7)-C(6) 1.364(5) C(18)-C(17)-P(1) 118.8(3) C(23)-C(24) 1.393(5) C(22)-C(17)-P(1) 122.0(3) C(23)-C(28) 1.394(5) C(13)-C(12)-C(11) 119.6(3) C(11)-C(16) 1.394(5) C(10)-C(9)-C(8) 121.4(3) C(6)-C(5) 1.423(5) C(9)-C(8)-C(7) 124.0(3) C(18)-C(19) 1.387(5) C(9)-C(8)-C(3) 117.8(3) C(5)-C(4) 1.380(5) C(7)-C(8)-C(3) 118.1(3) C(26)-C(27) 1.380(5) C(1)-C(2)-C(3) 123.4(3) C(26)-C(25) 1.388(6) C(6)-C(7)-C(8) 121.3(3) C(24)-C(25) 1.379(5) C(24)-C(23)-C(28) 119.2(3) C(19)-C(20) 1.383(6) C(24)-C(23)-P(1) 118.6(3) C(27)-C(28) 1.385(5) C(28)-C(23)-P(1) 122.1(3) C(13)-C(14) 1.373(6) C(16)-C(11)-C(12) 119.0(3) C(29)-C(30) 1.391(5) C(16)-C(11)-P(1) 119.1(3) C(29)-C(34) 1.395(5) C(12)-C(11)-P(1) 122.0(3) C(35)-C(36) 1.385(5) C(9)-C(10)-C(1) 122.2(3) C(35)-C(40) 1.393(5) C(7)-C(6)-C(5) 122.5(3) C(44)-C(45) 1.384(6) C(17)-C(18)-C(19) 120.6(3) C(44)-C(43) 1.387(6) C(4)-C(5)-C(6) 115.9(3) C(36)-C(37) 1.389(5) C(4)-C(5)-Au(2) 120.4(3) C(34)-C(33) 1.387(5) C(6)-C(5)-Au(2) 123.7(3) C(42)-C(43) 1.382(5) C(27)-C(26)-C(25) 120.3(3) C(40)-C(39) 1.395(5) C(25)-C(24)-C(23) 120.6(3) C(30)-C(31) 1.383(5) C(20)-C(19)-C(18) 119.8(3) C(46)-C(45) 1.394(5) C(28)-C(27)-C(26) 120.1(4) C(31)-C(32) 1.377(6) C(5)-C(4)-C(3) 123.9(3) C(20)-C(21) 1.377(6) C(27)-C(28)-C(23) 120.1(3) C(22)-C(21) 1.395(5) C(14)-C(13)-C(12) 121.2(4) C(16)-C(15) 1.384(5) C(24)-C(25)-C(26) 119.7(3) C(32)-C(33) 1.380(6) C(30)-C(29)-C(34) 119.4(3) C(37)-C(38) 1.378(6) C(30)-C(29)-P(2) 122.9(3) C(38)-C(39) 1.386(6) C(34)-C(29)-P(2) 117.6(3) C(14)-C(15) 1.378(6) C(36)-C(35)-C(40) 118.9(3) C(49)-C(48) 1.380(6) C(36)-C(35)-P(2) 117.8(3) C(49)-C(50) 1.378(6) C(40)-C(35)-P(2) 123.2(3) C(50)-C(51) 1.373(7) C(45)-C(44)-C(43) 119.4(4) C(47)-C(48) 1.364(7) C(35)-C(36)-C(37) 121.2(3)

241

C(47)-C(52) 1.376(7) C(33)-C(34)-C(29) 119.9(3) C(52)-C(51) 1.377(8) C(43)-C(42)-C(41) 120.7(3) C(35)-C(40)-C(39) 120.1(4) C(29)-C(30)-C(31) 119.8(3) C(41)-C(46)-C(45) 119.7(3) C(32)-C(31)-C(30) 120.7(4) C(42)-C(43)-C(44) 120.2(3) C(19)-C(20)-C(21) 120.2(4) C(21)-C(22)-C(17) 120.2(4) C(15)-C(16)-C(11) 120.2(4) C(31)-C(32)-C(33) 119.9(3) C(20)-C(21)-C(22) 120.0(4) C(38)-C(37)-C(36) 119.6(4) C(37)-C(38)-C(39) 120.1(4) C(13)-C(14)-C(15) 119.3(4) C(14)-C(15)-C(16) 120.7(4) C(34)-C(33)-C(32) 120.2(4) C(48)-C(49)-C(50) 119.8(4) C(51)-C(50)-C(49) 120.0(5) C(48)-C(47)-C(52) 120.2(5) C(47)-C(48)-C(49) 120.0(4) C(38)-C(39)-C(40) 120.1(4) C(44)-C(45)-C(46) 120.7(4) C(47)-C(52)-C(51) 120.1(5) C(50)-C(51)-C(52) 119.8(5)

242

7. X-Ray crystallographic data for [(SIPr)Au(2-naphthylethynyl)]

Table AI-7a. Crystallographic data for Table AI-7b. Data collection

MC121208

C39H45AuN2 Bruker SMART CCD area-detector

Mr = 738.74 diffractometer

Monoclinic, P21  scans

a = 12.8343(10) Å Absorption correction: multi-scan

b = 10.3083(8) Å Tmin = 0.3544, Tmax = 0.4343

c = 15.8854(13) Å 21070 measured reflections

α = 90.00 º 8077 independent reflections

 = 113.7940(10) º 7726 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0234

3 V = 1923.0(3) Å  max = 26.86º

Z = 2 h = -16  16

-3 Dx = 1.276 Mg m k = -12  13

Mo K radiation l = -20  20

Cell parameters from 9964 reflections

 = 1.73±26.86º

 = 3.850 mm-1

T = 100 (2) K

Irregular, colorless

0.34  0.27 0.26 mm

243

Table AI-7c. Refinement Figure AI-7a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0241 wR(F2) = 0.0579

S = 1.036

8077 reflections

387 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0000P) + 3.9877P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.096

-3 max = 1.059 eÅ

-3 min = -0.597 eÅ

Table AI-7d. Selected geometric parameters (Å, º). Au(1)-C(1) 1.994(4) C(1)-Au(1)-C(13) 179.4(5) Au(1)-C(13) 1.999(3) C(2)-C(1)-Au(1) 175.0(10) C(1)-C(2) 1.171(5) C(13)-N(2)-C(28) 123.7(3) N(2)-C(13) 1.330(4) C(13)-N(2)-C(15) 113.7(3) N(2)-C(28) 1.421(5) C(28)-N(2)-C(15) 122.1(3) N(2)-C(15) 1.472(5) N(2)-C(13)-N(1) 107.8(3) C(13)-N(1) 1.360(4) N(2)-C(13)-Au(1) 126.9(2) N(1)-C(16) 1.427(5) N(1)-C(13)-Au(1) 125.3(2) N(1)-C(14) 1.468(5) C(13)-N(1)-C(16) 123.8(3) C(18)-C(19) 1.361(7) C(13)-N(1)-C(14) 112.9(3) C(18)-C(17) 1.394(6) C(16)-N(1)-C(14) 122.1(3) C(17)-C(16) 1.391(6) C(19)-C(18)-C(17) 122.0(4) C(17)-C(22) 1.508(7) C(16)-C(17)-C(18) 117.0(4) C(3)-C(4) 1.356(9) C(16)-C(17)-C(22) 121.5(4) C(3)-C(12) 1.413(9) C(18)-C(17)-C(22) 121.4(4) C(3)-C(2) 1.465(6) C(4)-C(3)-C(12) 118.8(5) C(21)-C(20) 1.383(6) C(4)-C(3)-C(2) 120.7(8)

244

C(21)-C(16) 1.402(6) C(12)-C(3)-C(2) 120.2(7) C(21)-C(25) 1.514(7) C(1)-C(2)-C(3) 176.3(7) C(20)-C(19) 1.392(7) C(20)-C(21)-C(16) 117.8(4) C(15)-C(14) 1.536(6) C(20)-C(21)-C(25) 119.8(5) C(29)-C(28) 1.394(6) C(16)-C(21)-C(25) 122.4(4) C(29)-C(30) 1.404(6) C(17)-C(16)-C(21) 122.5(4) C(29)-C(34) 1.524(6) C(17)-C(16)-N(1) 118.5(4) C(34)-C(35) 1.517(8) C(21)-C(16)-N(1) 119.0(4) C(34)-C(36) 1.517(7) C(21)-C(20)-C(19) 120.7(4) C(33)-C(32) 1.387(7) N(2)-C(15)-C(14) 102.2(3) C(33)-C(28) 1.393(6) N(1)-C(14)-C(15) 102.2(3) C(33)-C(37) 1.503(7) C(28)-C(29)-C(30) 116.3(5) C(37)-C(39) 1.534(7) C(28)-C(29)-C(34) 122.4(4) C(37)-C(38) 1.537(8) C(30)-C(29)-C(34) 121.2(5) C(32)-C(31) 1.369(7) C(35)-C(34)-C(36) 110.6(4) C(25)-C(27) 1.518(8) C(35)-C(34)-C(29) 111.0(4) C(25)-C(26) 1.534(7) C(36)-C(34)-C(29) 112.7(4) C(30)-C(31) 1.343(10) C(32)-C(33)-C(28) 117.9(4) C(22)-C(24) 1.525(7) C(32)-C(33)-C(37) 120.4(4) C(22)-C(23) 1.536(9) C(28)-C(33)-C(37) 121.6(4) C(12)-C(11) 1.400(8) C(33)-C(28)-C(29) 122.1(4) C(5)-C(6) 1.371(8) C(33)-C(28)-N(2) 119.2(4) C(5)-C(4) 1.401(8) C(29)-C(28)-N(2) 118.6(4) C(6)-C(11) 1.383(9) C(33)-C(37)-C(39) 111.6(4) C(6)-C(7) 1.453(8) C(33)-C(37)-C(38) 110.2(4) C(11)-C(10) 1.414(9) C(39)-C(37)-C(38) 110.3(4) C(10)-C(9) 1.366(10) C(31)-C(32)-C(33) 121.1(5) C(8)-C(7) 1.337(10) C(21)-C(25)-C(27) 110.4(4) C(8)-C(9) 1.386(12) C(21)-C(25)-C(26) 110.5(4) C(27)-C(25)-C(26) 110.3(4) C(31)-C(30)-C(29) 122.5(5) C(30)-C(31)-C(32) 120.1(4) C(18)-C(19)-C(20) 120.0(4) C(17)-C(22)-C(24) 113.2(5) C(17)-C(22)-C(23) 109.6(4) C(24)-C(22)-C(23) 109.5(5) C(11)-C(12)-C(3) 121.4(6) C(6)-C(5)-C(4) 120.9(6) C(5)-C(6)-C(11) 120.8(6) C(5)-C(6)-C(7) 121.7(6) C(11)-C(6)-C(7) 117.5(6) C(6)-C(11)-C(12) 117.9(6) C(6)-C(11)-C(10) 119.9(6) C(12)-C(11)-C(10) 122.2(6)

245

C(9)-C(10)-C(11) 119.1(7) C(3)-C(4)-C(5) 120.0(7) C(7)-C(8)-C(9) 118.1(7) C(10)-C(9)-C(8) 122.9(7) C(8)-C(7)-C(6) 122.4(7)

246

8. X-Ray crystallographic data for [(SIPr)Au(ferrocenylethynyl)]

Table AI-8a. Crystallographic data for Table AI-8b. Data collection

ND121808B

C39H47AuFeN2 Bruker SMART CCD area-detector

Mr = 796.60 diffractometer

Orthorhombic, P212121  scans

a = 12.2581(8) Å Absorption correction: multi-scan

b = 14.5555(9) Å Tmin = 0.2673, Tmax = 0.3704

c = 19.8593(12) Å 42076 measured reflections

α = 90.00 º 8327 independent reflections

 = 90.00 º 7962 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0229

3 V = 3543.4(4) Å  max = 27.93º

Z = 4 h = -15  16

-3 Dx = 1.493 Mg m k = -18  19

Mo K radiation l = -25  26

Cell parameters from 9786 reflections

 = 1.73±27.93º

 = 4.573 mm-1

T = 100 (2) K

Irregular, red

0.39  0.30 0.27 mm

247

Table AI-8c. Refinement Figure AI-8a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0144 wR(F2) = 0.0373

S = 1.003

8327 reflections

396 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0145P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.061

-3 max = 1.059 eÅ

-3 min = -0.582 eÅ

Table AI-8d. Selected geometric parameters (Å, º). Au(1)-C(1) 1.988(2) C(1)-Au(1)-C(13) 174.23(8) Au(1)-C(13) 2.0132(19) C(12)-Fe(1)-C(8) 41.50(17) Fe(1)-C(12) 2.016(3) C(12)-Fe(1)-C(5) 155.05(18) Fe(1)-C(8) 2.018(3) C(8)-Fe(1)-C(5) 161.83(16) Fe(1)-C(5) 2.030(2) C(12)-Fe(1)-C(4) 163.28(18) Fe(1)-C(4) 2.031(2) C(8)-Fe(1)-C(4) 124.15(14) Fe(1)-C(9) 2.034(3) C(5)-Fe(1)-C(4) 40.97(10) Fe(1)-C(11) 2.036(3) C(12)-Fe(1)-C(9) 67.92(15) Fe(1)-C(10) 2.038(3) C(8)-Fe(1)-C(9) 39.92(13) Fe(1)-C(7) 2.038(2) C(5)-Fe(1)-C(9) 125.60(13) Fe(1)-C(6) 2.043(2) C(4)-Fe(1)-C(9) 106.35(12) Fe(1)-C(3) 2.043(2) C(12)-Fe(1)-C(11) 41.08(16) N(2)-C(13) 1.338(2) C(8)-Fe(1)-C(11) 68.95(15) N(2)-C(28) 1.438(2) C(5)-Fe(1)-C(11) 119.80(14) N(2)-C(15) 1.474(2) C(4)-Fe(1)-C(11) 152.97(15) N(1)-C(13) 1.339(2) C(9)-Fe(1)-C(11) 67.36(13) N(1)-C(16) 1.440(2) C(12)-Fe(1)-C(10) 67.90(15)

248

N(1)-C(14) 1.482(2) C(8)-Fe(1)-C(10) 68.16(14) C(28)-C(29) 1.397(3) C(5)-Fe(1)-C(10) 107.60(12) C(28)-C(33) 1.403(3) C(4)-Fe(1)-C(10) 118.67(14) C(33)-C(32) 1.394(3) C(9)-Fe(1)-C(10) 40.43(12) C(33)-C(37) 1.521(3) C(11)-Fe(1)-C(10) 39.44(14) C(15)-C(14) 1.523(3) C(12)-Fe(1)-C(7) 108.43(14) C(1)-C(2) 1.204(3) C(8)-Fe(1)-C(7) 119.47(12) C(16)-C(21) 1.388(3) C(5)-Fe(1)-C(7) 69.22(10) C(16)-C(17) 1.406(3) C(4)-Fe(1)-C(7) 69.17(10) C(31)-C(32) 1.382(3) C(9)-Fe(1)-C(7) 153.24(11) C(31)-C(30) 1.395(3) C(11)-Fe(1)-C(7) 128.41(13) C(35)-C(34) 1.526(3) C(10)-Fe(1)-C(7) 165.02(12) C(18)-C(19) 1.367(4) C(12)-Fe(1)-C(6) 120.92(16) C(18)-C(17) 1.395(3) C(8)-Fe(1)-C(6) 155.38(15) C(30)-C(29) 1.388(3) C(5)-Fe(1)-C(6) 40.94(11) C(22)-C(17) 1.507(3) C(4)-Fe(1)-C(6) 68.85(11) C(22)-C(23) 1.533(3) C(9)-Fe(1)-C(6) 163.94(13) C(22)-C(24) 1.542(3) C(11)-Fe(1)-C(6) 109.52(12) C(29)-C(34) 1.524(3) C(10)-Fe(1)-C(6) 127.23(12) C(21)-C(20) 1.409(3) C(7)-Fe(1)-C(6) 41.01(9) C(21)-C(25) 1.516(3) C(12)-Fe(1)-C(3) 126.21(16) C(2)-C(3) 1.441(3) C(8)-Fe(1)-C(3) 105.98(11) C(20)-C(19) 1.377(4) C(5)-Fe(1)-C(3) 69.30(9) C(34)-C(36) 1.531(3) C(4)-Fe(1)-C(3) 41.25(9) C(38)-C(37) 1.527(3) C(9)-Fe(1)-C(3) 118.18(10) C(25)-C(26) 1.526(3) C(11)-Fe(1)-C(3) 165.35(14) C(25)-C(27) 1.535(3) C(10)-Fe(1)-C(3) 152.92(13) C(37)-C(39) 1.524(3) C(7)-Fe(1)-C(3) 41.04(9) C(4)-C(5) 1.421(3) C(6)-Fe(1)-C(3) 69.01(9) C(4)-C(3) 1.435(3) C(13)-N(2)-C(28) 124.85(15) C(7)-C(6) 1.429(3) C(13)-N(2)-C(15) 113.35(15) C(7)-C(3) 1.430(3) C(28)-N(2)-C(15) 121.17(15) C(5)-C(6) 1.425(4) C(13)-N(1)-C(16) 126.44(15) C(9)-C(8) 1.383(5) C(13)-N(1)-C(14) 112.75(15) C(9)-C(10) 1.407(4) C(16)-N(1)-C(14) 118.32(15) C(12)-C(11) 1.422(6) C(29)-C(28)-C(33) 123.24(18) C(12)-C(8) 1.429(6) C(29)-C(28)-N(2) 119.33(17) C(10)-C(11) 1.375(5) C(33)-C(28)-N(2) 117.42(17) C(32)-C(33)-C(28) 117.23(19) C(32)-C(33)-C(37) 120.96(18) C(28)-C(33)-C(37) 121.75(18) N(2)-C(13)-N(1) 107.21(16) N(2)-C(13)-Au(1) 123.21(13) N(1)-C(13)-Au(1) 129.51(13)

249

N(2)-C(15)-C(14) 101.28(15) C(2)-C(1)-Au(1) 172.45(19) C(21)-C(16)-C(17) 123.77(19) C(21)-C(16)-N(1) 119.29(19) C(17)-C(16)-N(1) 116.75(18) C(32)-C(31)-C(30) 120.84(19) N(1)-C(14)-C(15) 101.27(15) C(31)-C(32)-C(33) 120.7(2) C(31)-C(32)-H(32) 119.7 C(19)-C(18)-C(17) 121.0(2) C(29)-C(30)-C(31) 120.5(2) C(17)-C(22)-C(23) 110.46(18) C(17)-C(22)-C(24) 113.8(2) C(23)-C(22)-C(24) 110.22(18) C(30)-C(29)-C(28) 117.51(18) C(30)-C(29)-C(34) 120.31(18) C(28)-C(29)-C(34) 122.18(18) C(18)-C(17)-C(16) 116.7(2) C(18)-C(17)-C(22) 122.2(2) C(16)-C(17)-C(22) 121.05(18) C(16)-C(21)-C(20) 116.6(2) C(16)-C(21)-C(25) 123.32(19) C(20)-C(21)-C(25) 120.0(2) C(1)-C(2)-C(3) 176.0(2) C(19)-C(20)-C(21) 120.5(2) C(29)-C(34)-C(35) 110.79(19) C(29)-C(34)-C(36) 111.50(17) C(35)-C(34)-C(36) 110.71(19) C(21)-C(25)-C(26) 111.7(2) C(21)-C(25)-C(27) 112.0(2) C(26)-C(25)-C(27) 110.7(2) C(33)-C(37)-C(39) 112.84(18) C(33)-C(37)-C(38) 109.51(17) C(39)-C(37)-C(38) 110.78(18) C(33)-C(37)-H(37) 107.8 C(5)-C(4)-C(3) 108.3(2) C(5)-C(4)-Fe(1) 69.48(14) C(3)-C(4)-Fe(1) 69.80(13) C(6)-C(7)-C(3) 108.1(2) C(6)-C(7)-Fe(1) 69.68(14) C(3)-C(7)-Fe(1) 69.67(13) C(18)-C(19)-C(20) 121.4(2) C(7)-C(3)-C(4) 107.4(2) C(7)-C(3)-C(2) 127.2(2)

250

C(4)-C(3)-C(2) 125.4(2) C(7)-C(3)-Fe(1) 69.29(13) C(4)-C(3)-Fe(1) 68.95(13) C(2)-C(3)-Fe(1) 124.76(16) C(4)-C(5)-C(6) 108.1(2) C(4)-C(5)-Fe(1) 69.55(13) C(6)-C(5)-Fe(1) 69.99(14) C(5)-C(6)-C(7) 108.1(2) C(5)-C(6)-Fe(1) 69.07(13) C(7)-C(6)-Fe(1) 69.31(13) C(8)-C(9)-C(10) 109.1(3) C(8)-C(9)-Fe(1) 69.43(18) C(10)-C(9)-Fe(1) 69.92(16) C(11)-C(12)-C(8) 107.2(3) C(11)-C(12)-Fe(1) 70.23(19) C(8)-C(12)-Fe(1) 69.33(18) C(11)-C(10)-C(9) 108.5(3) C(11)-C(10)-Fe(1) 70.23(18) C(9)-C(10)-Fe(1) 69.64(16) C(9)-C(8)-C(12) 107.1(3) C(9)-C(8)-Fe(1) 70.65(17) C(12)-C(8)-Fe(1) 69.17(18) C(10)-C(11)-C(12) 108.1(3) C(10)-C(11)-Fe(1) 70.33(17) C(12)-C(11)-Fe(1) 68.69(18)

251

9. X-Ray crystallographic data for [(SIPr)Au(1-pyrenylethynyl)]

Table AI-9a. Crystallographic data for Table AI-9b. Data collection

JU093008

C45H47AuN2 Bruker SMART CCD area-detector

Mr = 812.81 diffractometer

Monoclinic, P21/n  scans

a = 15.340(3) Å Absorption correction: multi-scan

b = 10.7795(19) Å Tmin = 0.2725, Tmax = 0.6153

c = 25.587(4)Å 48069 measured reflections

α = 90.00 º 9598 independent reflections

 = 102.112(2) º 8788 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0265

3 V = 4136.8(13) Å  max = 27.82º

Z = 4 h = -19  19

-3 Dx = 1.305 Mg m k = -13  14

Mo K radiation l = -33 33

Cell parameters from 9665 reflections

 = 1.43±27.82º

 = 4.573 mm-1

T = 100 (2) K

Irregular, colorless

0.49  0.36 0.15 mm

252

Table AI-9c. Refinement Figure AI-9a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0189 wR(F2) = 0.0879

S = 0.800

9598 reflections

441 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.1000P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.100 -3 max = 0.683 eÅ

-3 min = -0.437 eÅ

Table AI-9d. Selected geometric parameters (Å, º). Au(1)-C(1) 1.992(3) C(1)-Au(1)-C(19) 177.52(8) Au(1)-C(19) 2.026(3) C(19)-N(1)-C(22) 124.3(2) N(1)-C(19) 1.329(3) C(19)-N(1)-C(20) 113.1(2) N(1)-C(22) 1.436(3) C(22)-N(1)-C(20) 120.77(17) N(1)-C(20) 1.480(3) C(19)-N(2)-C(34) 125.4(2) N(2)-C(19) 1.339(3) C(19)-N(2)-C(21) 112.9(2) N(2)-C(34) 1.435(3) C(34)-N(2)-C(21) 121.40(18) N(2)-C(21) 1.471(3) C(2)-C(1)-Au(1) 174.1(2) C(1)-C(2) 1.221(4) N(1)-C(19)-N(2) 108.4(2) C(28)-C(29) 1.518(4) N(1)-C(19)-Au(1) 126.3(2) C(28)-C(23) 1.526(3) N(2)-C(19)-Au(1) 125.2(2) C(28)-C(30) 1.537(4) C(29)-C(28)-C(23) 112.4(2) C(27)-C(26) 1.389(3) C(29)-C(28)-C(30) 110.3(2) C(27)-C(22) 1.399(3) C(23)-C(28)-C(30) 110.41(19) C(27)-C(31) 1.528(3) C(26)-C(27)-C(22) 117.5(2) C(20)-C(21) 1.535(3) C(26)-C(27)-C(31) 122.2(2) C(24)-C(25) 1.367(3) C(22)-C(27)-C(31) 120.35(19)

253

C(24)-C(23) 1.392(3) N(1)-C(20)-C(21) 101.46(19) C(18)-C(13) 1.417(3) C(25)-C(24)-C(23) 121.1(2) C(18)-C(9) 1.419(4) C(13)-C(18)-C(9) 120.0(2) C(18)-C(17) 1.427(3) C(13)-C(18)-C(17) 120.0(2) C(14)-C(15) 1.351(3) C(9)-C(18)-C(17) 120.0(2) C(14)-C(13) 1.434(3) C(15)-C(14)-C(13) 121.4(2) C(15)-C(16) 1.432(3) N(2)-C(21)-C(20) 102.14(19) C(9)-C(10) 1.397(3) C(14)-C(15)-C(16) 121.5(2) C(9)-C(8) 1.441(4) C(10)-C(9)-C(18) 119.2(3) C(22)-C(23) 1.404(3) C(10)-C(9)-C(8) 122.1(3) C(13)-C(12) 1.401(3) C(18)-C(9)-C(8) 118.8(2) C(3)-C(4) 1.403(3) C(27)-C(22)-C(23) 122.7(2) C(3)-C(16) 1.415(3) C(27)-C(22)-N(1) 118.41(18) C(3)-C(2) 1.427(3) C(23)-C(22)-N(1) 118.81(19) C(25)-C(26) 1.385(3) C(12)-C(13)-C(18) 119.1(2) C(6)-C(5) 1.395(4) C(12)-C(13)-C(14) 122.3(2) C(6)-C(17) 1.420(3) C(18)-C(13)-C(14) 118.6(2) C(6)-C(7) 1.437(3) C(4)-C(3)-C(16) 119.0(2) C(16)-C(17) 1.421(3) C(4)-C(3)-C(2) 120.7(2) C(8)-C(7) 1.340(4) C(16)-C(3)-C(2) 120.2(2) C(5)-C(4) 1.380(4) C(24)-C(25)-C(26) 121.0(2) C(11)-C(12) 1.386(4) C(24)-C(23)-C(22) 117.1(2) C(11)-C(10) 1.391(4) C(24)-C(23)-C(28) 120.9(2) C(31)-C(33) 1.525(3) C(22)-C(23)-C(28) 122.0(2) C(31)-C(32) 1.528(3) C(5)-C(6)-C(17) 118.5(2) C(36)-C(37) 1.371(4) C(5)-C(6)-C(7) 122.5(2) C(36)-C(35) 1.398(3) C(17)-C(6)-C(7) 119.0(2) C(35)-C(34) 1.393(3) C(3)-C(16)-C(17) 119.3(2) C(35)-C(40) 1.516(3) C(3)-C(16)-C(15) 122.2(2) C(34)-C(39) 1.406(3) C(17)-C(16)-C(15) 118.6(2) C(37)-C(38) 1.378(4) C(25)-C(26)-C(27) 120.6(2) C(39)-C(38) 1.394(3) C(1)-C(2)-C(3) 175.8(3) C(39)-C(43) 1.532(3) C(7)-C(8)-C(9) 121.2(2) C(41)-C(40) 1.535(5) C(8)-C(7)-C(6) 121.4(2) C(40)-C(42) 1.526(4) C(6)-C(17)-C(16) 120.5(2) C(43)-C(45) 1.483(5) C(6)-C(17)-C(18) 119.5(2) C(43)-C(44) 1.496(4) C(16)-C(17)-C(18) 119.9(2) C(4)-C(5)-C(6) 121.3(2) C(12)-C(11)-C(10) 120.6(2) C(5)-C(4)-C(3) 121.3(2) C(11)-C(12)-C(13) 120.6(3) C(11)-C(10)-C(9) 120.5(2) C(33)-C(31)-C(27) 111.87(19) C(33)-C(31)-C(32) 109.5(2)

254

C(27)-C(31)-C(32) 113.15(19) C(37)-C(36)-C(35) 121.1(2) C(34)-C(35)-C(36) 117.5(2) C(34)-C(35)-C(40) 122.0(2) C(36)-C(35)-C(40) 120.5(2) C(35)-C(34)-C(39) 122.6(2) C(35)-C(34)-N(2) 118.9(2) C(39)-C(34)-N(2) 118.56(19) C(36)-C(37)-C(38) 120.4(2) C(38)-C(39)-C(34) 117.1(2) C(38)-C(39)-C(43) 121.1(2) C(34)-C(39)-C(43) 121.8(2) C(37)-C(38)-C(39) 121.3(2) C(35)-C(40)-C(42) 111.1(2) C(35)-C(40)-C(41) 111.1(2) C(42)-C(40)-C(41) 111.4(3) C(45)-C(43)-C(44) 110.6(3) C(45)-C(43)-C(39) 112.2(2) C(44)-C(43)-C(39) 111.9(2)

255

10. X-Ray crystallographic data for [(SIPr)Au(1-benzyl-4-(2-naphthy)triazolato)]

Table AI-10a. Crystallographic data for Table AI-10b. Data collection

JU092408

2(C46H52AuN5·C6H6) Bruker SMART CCD area-detector

Mr = 1900.00 diffractometer

Triclinic, Pī  scans

a = 11.3686(11) Å Absorption correction: multi-scan

b = 12.6375(13) Å Tmin = 0.6275, Tmax = 0.7457

c = 16.3123(16) Å 24345 measured reflections

α = 103.1030(10) º 9301 independent reflections

 = 101.8910(10) º 9000 reflections with I > 2(I)

γ = 95.3870(10) º Rint =0.0228

3 V = 2209.2(4) Å  max = 26.94º

Z = 1 h = -14  14

-3 Dx = 1.428 Mg m k = -15  15

Mo K radiation l = -20  20

Cell parameters from 9884 reflections

 = 1.32±26.94º

 = 3.371 mm-1

T = 100 (2) K

Irregular, colorless

0.49  0.47 0.44 mm

256

Table AI-10c. Refinement Figure AI-10a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent molecules are

omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0248 wR(F2) = 0.0844

S = 1.233

9301 reflections

531 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0440P) + 3.7364P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.144

-3 max = 0.683 eÅ

-3 min = -1.456 eÅ

Table AI-10d. Selected geometric parameters (Å, º). Au(1)-C(20) 2.015(3) C(20)-Au(1)-C(1) 175.06(13) Au(1)-C(1) 2.018(3) N(2)-N(1)-C(1) 113.2(3) N(1)-N(2) 1.339(4) N(2)-N(1)-C(13) 118.4(3) N(1)-C(1) 1.367(5) C(1)-N(1)-C(13) 128.2(3) N(1)-C(13) 1.442(5) N(3)-N(2)-N(1) 106.5(3) N(2)-N(3) 1.304(5) N(2)-N(3)-C(2) 108.9(3) N(3)-C(2) 1.362(5) C(20)-N(4)-C(23) 127.0(3) N(4)-C(20) 1.328(4) C(20)-N(4)-C(22) 112.5(3) N(4)-C(23) 1.434(4) C(23)-N(4)-C(22) 120.0(3) N(4)-C(22) 1.480(4) C(20)-N(5)-C(35) 125.0(3) N(5)-C(20) 1.330(4) C(20)-N(5)-C(21) 112.5(3) N(5)-C(35) 1.435(4) C(35)-N(5)-C(21) 119.0(3) N(5)-C(21) 1.468(4) N(1)-C(1)-C(2) 101.4(3) C(1)-C(2) 1.380(5) N(1)-C(1)-Au(1) 120.2(3) C(2)-C(3) 1.462(5) C(2)-C(1)-Au(1) 137.9(3)

257

C(3)-C(12) 1.368(5) N(3)-C(2)-C(1) 110.0(3) C(3)-C(4) 1.420(6) N(3)-C(2)-C(3) 119.1(3) C(4)-C(5) 1.358(6) C(1)-C(2)-C(3) 130.8(4) C(5)-C(6) 1.418(6) C(12)-C(3)-C(4) 118.3(4) C(6)-C(11) 1.406(6) C(12)-C(3)-C(2) 120.1(4) C(6)-C(7) 1.422(6) C(4)-C(3)-C(2) 121.6(3) C(7)-C(8) 1.366(7) C(5)-C(4)-C(3) 121.0(4) C(8)-C(9) 1.399(8) C(4)-C(5)-C(6) 121.0(4) C(9)-C(10) 1.356(7) C(11)-C(6)-C(5) 118.5(4) C(10)-C(11) 1.421(6) C(11)-C(6)-C(7) 119.0(4) C(11)-C(12) 1.411(6) C(5)-C(6)-C(7) 122.5(4) C(13)-C(14) 1.511(5) C(8)-C(7)-C(6) 120.5(5) C(14)-C(19) 1.377(6) C(7)-C(8)-C(9) 120.2(4) C(14)-C(15) 1.379(6) C(10)-C(9)-C(8) 120.9(5) C(15)-C(16) 1.390(6) C(9)-C(10)-C(11) 120.5(5) C(16)-C(17) 1.373(7) C(6)-C(11)-C(12) 119.1(4) C(17)-C(18) 1.359(8) C(6)-C(11)-C(10) 119.0(4) C(18)-C(19) 1.377(7) C(12)-C(11)-C(10) 121.9(4) C(21)-C(22) 1.522(5) C(3)-C(12)-C(11) 122.1(4) C(23)-C(24) 1.391(5) N(1)-C(13)-C(14) 113.6(3) C(23)-C(28) 1.395(5) C(19)-C(14)-C(15) 119.1(4) C(24)-C(25) 1.396(5) C(19)-C(14)-C(13) 118.1(4) C(24)-C(29) 1.519(5) C(15)-C(14)-C(13) 122.8(4) C(25)-C(26) 1.382(6) C(14)-C(15)-C(16) 120.2(4) C(26)-C(27) 1.377(6) C(17)-C(16)-C(15) 119.6(5) C(27)-C(28) 1.398(5) C(18)-C(17)-C(16) 120.3(4) C(28)-C(32) 1.512(5) C(17)-C(18)-C(19) 120.4(5) C(29)-C(31) 1.520(6) C(18)-C(19)-C(14) 120.4(5) C(29)-C(30) 1.525(6) N(4)-C(20)-N(5) 108.8(3) C(32)-C(34) 1.521(6) N(4)-C(20)-Au(1) 126.1(2) C(32)-C(33) 1.521(6) N(5)-C(20)-Au(1) 125.0(3) C(35)-C(36) 1.387(5) N(5)-C(21)-C(22) 102.1(3) C(35)-C(40) 1.404(5) N(4)-C(22)-C(21) 101.6(3) C(36)-C(37) 1.390(5) C(24)-C(23)-C(28) 123.1(3) C(36)-C(41) 1.519(5) C(24)-C(23)-N(4) 118.6(3) C(37)-C(38) 1.375(6) C(28)-C(23)-N(4) 118.2(3) C(38)-C(39) 1.377(6) C(23)-C(24)-C(25) 117.2(4) C(39)-C(40) 1.387(5) C(23)-C(24)-C(29) 122.6(3) C(40)-C(44) 1.520(6) C(25)-C(24)-C(29) 120.2(3) C(41)-C(42) 1.527(5) C(26)-C(25)-C(24) 121.0(4) C(41)-C(43) 1.528(5) C(27)-C(26)-C(25) 120.5(4) C(44)-C(46) 1.521(6) C(26)-C(27)-C(28) 120.7(4) C(44)-C(45) 1.523(6) C(23)-C(28)-C(27) 117.4(4) C(93)-C(94) 1.390(10) C(23)-C(28)-C(32) 121.8(3)

258

C(93)-C(98) 1.427(12) C(27)-C(28)-C(32) 120.8(3) C(94)-C(95) 1.345(8) C(24)-C(29)-C(31) 110.9(3) C(95)-C(96) 1.340(8) C(24)-C(29)-C(30) 112.6(3) C(96)-C(97) 1.343(9) C(31)-C(29)-C(30) 110.2(4) C(97)-C(98) 1.352(11) C(28)-C(32)-C(34) 111.1(3) C(28)-C(32)-C(33) 113.0(3) C(34)-C(32)-C(33) 109.4(3) C(36)-C(35)-C(40) 122.5(3) C(36)-C(35)-N(5) 119.9(3) C(40)-C(35)-N(5) 117.5(3) C(35)-C(36)-C(37) 117.4(4) C(35)-C(36)-C(41) 123.0(3) C(37)-C(36)-C(41) 119.6(3) C(38)-C(37)-C(36) 121.5(4) C(37)-C(38)-C(39) 120.0(4) C(37)-C(38)-H(38) 120.0 C(38)-C(39)-C(40) 121.2(4) C(39)-C(40)-C(35) 117.4(4) C(39)-C(40)-C(44) 121.9(3) C(35)-C(40)-C(44) 120.6(3) C(36)-C(41)-C(42) 110.9(3) C(36)-C(41)-C(43) 111.5(3) C(42)-C(41)-C(43) 111.9(3) C(40)-C(44)-C(46) 110.2(4) C(40)-C(44)-C(45) 113.5(3) C(46)-C(44)-C(45) 110.5(4) C(94)-C(93)-C(98) 117.6(6) C(95)-C(94)-C(93) 120.0(6) C(96)-C(95)-C(94) 121.4(6) C(95)-C(96)-C(97) 120.9(6) C(96)-C(97)-C(98) 120.9(6) C(97)-C(98)-C(93) 119.2(6)

259

11. X-Ray crystallographic data for [(SIPr)Au(1-benzyl-4-tert-butyltriazolato)]

Table AI-11a. Crystallographic data for Table AI-11b. Data collection

JU100708

C43H48AuN5 Bruker SMART CCD area-detector

Mr = 831.83 diffractometer

Monoclinic, P21/c  scans

a = 12.124(2) Å Absorption correction: multi-scan

b = 15.310(3) Å Tmin = 0.2320, Tmax = 0.6661

c = 22.237(4) Å 46592 measured reflections

α = 90.00 º 9256 independent reflections

 = 102.582(2) º 7789 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0560

3 V = 4028.4(14) Å  max = 27.50º

Z = 4 h = -15  15

-3 Dx = 1.372 Mg m k = -19  19

Mo K radiation l = -28  28

Cell parameters from 9930 reflections

 = 1.63±27.50º

 = 3.686 mm-1

T = 100 (2) K

Irregular, colorless

0.56  0.21 0.12 mm

260

Table AI-11c. Refinement Figure AI-11a. ORTEP plot of title

compound. Ellipsoids are at the 50%

probability level. The labels of H atoms are

omitted for clarity. Tert-butyl groups exhibit

disorders, which are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0744 wR(F2) = 0.1799

S = 0.995

9256 reflections

457 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0798P) + 105.8440P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.224

-3 max = 5.156 eÅ

-3 min = -3.855 eÅ

Table AI-11d. Selected geometric parameters (Å, º). C(4)-C(3) 1.37(2) C(3)-C(4)-C(5) 124.7(12) C(4)-C(5) 1.3900 C(3)-C(4)-C(9) 115.2(12) C(4)-C(9) 1.3900 C(5)-C(4)-C(9) 120.0 C(5)-C(6) 1.3900 C(6)-C(5)-C(4) 120.0 C(6)-C(7) 1.3900 C(14)-Au(1)-C(1) 178.7(4) C(7)-C(8) 1.3900 N(5)-C(14)-N(4) 106.8(7) C(8)-C(9) 1.3900 N(5)-C(14)-Au(1) 124.9(6) Au(1)-C(14) 2.000(8) N(4)-C(14)-Au(1) 128.3(6) Au(1)-C(1) 2.007(12) C(14)-N(5)-C(29) 124.3(7) C(14)-N(5) 1.340(10) C(14)-N(5)-C(16) 114.6(7) C(14)-N(4) 1.345(11) C(29)-N(5)-C(16) 121.1(7) N(5)-C(29) 1.432(10) N(3)-C(2)-C(1) 108.8(17) N(5)-C(16) 1.469(12) N(3)-C(2)-C(10) 121.1(16) C(2)-N(3) 1.363(17) C(1)-C(2)-C(10) 130.1(10)

261

C(2)-C(1) 1.41(2) N(2)-N(1)-C(1) 114.6(15) C(2)-C(10) 1.49(2) N(2)-N(1)-C(3) 117.8(13) N(1)-N(2) 1.347(19) C(1)-N(1)-C(3) 127.5(13) N(1)-C(1) 1.356(15) N(2)-N(3)-C(2) 110.7(16) N(1)-C(3) 1.41(2) N(3)-N(2)-N(1) 105.4(12) N(3)-N(2) 1.28(3) N(1)-C(1)-C(2) 100.4(11) C(15)-N(4) 1.446(13) N(1)-C(1)-Au(1) 122.5(12) C(15)-C(16) 1.521(13) C(2)-C(1)-Au(1) 137.0(10) C(17)-C(18) 1.398(16) N(4)-C(15)-C(16) 104.1(8) C(17)-C(22) 1.403(15) C(18)-C(17)-C(22) 122.0(9) C(17)-N(4) 1.429(11) C(18)-C(17)-N(4) 119.3(9) C(22)-C(21) 1.397(15) C(22)-C(17)-N(4) 118.5(10) C(22)-C(26) 1.505(18) C(21)-C(22)-C(17) 117.8(12) C(18)-C(19) 1.402(14) C(21)-C(22)-C(26) 120.2(11) C(18)-C(23) 1.57(2) C(17)-C(22)-C(26) 122.0(10) C(29)-C(34) 1.374(16) C(17)-C(18)-C(19) 117.1(12) C(29)-C(30) 1.374(16) C(17)-C(18)-C(23) 121.1(9) C(26)-C(27) 1.521(17) C(19)-C(18)-C(23) 121.5(12) C(26)-C(28) 1.542(17) C(14)-N(4)-C(17) 125.3(8) C(19)-C(20) 1.36(2) C(14)-N(4)-C(15) 113.4(7) C(20)-C(21) 1.38(2) C(17)-N(4)-C(15) 121.3(8) C(34)-C(33) 1.392(19) C(34)-C(29)-C(30) 123.3(11) C(34)-C(35) 1.56(3) C(34)-C(29)-N(5) 117.9(10) C(23)-C(25) 1.54(2) C(30)-C(29)-N(5) 118.7(10) C(23)-C(24) 1.58(3) N(5)-C(16)-C(15) 101.0(8) C(30)-C(31) 1.405(18) C(22)-C(26)-C(27) 112.3(10) C(30)-C(38) 1.45(2) C(22)-C(26)-C(28) 113.2(12) C(31)-C(32) 1.33(3) C(27)-C(26)-C(28) 110.1(13) C(10)-C(12A) 1.40(3) C(20)-C(19)-C(18) 121.8(13) C(10)-C(11A) 1.48(3) C(19)-C(20)-C(21) 120.2(10) C(10)-C(13A) 1.50(3) C(29)-C(34)-C(33) 116.5(16) C(10)-C(12) 1.56(3) C(29)-C(34)-C(35) 121.8(11) C(10)-C(13) 1.62(3) C(33)-C(34)-C(35) 121.6(15) C(10)-C(11) 1.71(4) C(20)-C(21)-C(22) 121.0(12) C(35)-C(36) 1.42(4) C(25)-C(23)-C(18) 109.2(19) C(35)-C(37) 1.54(3) C(25)-C(23)-C(24) 113.5(18) C(32)-C(33) 1.37(3) C(18)-C(23)-C(24) 110.1(12) C(38)-C(39) 1.43(4) C(4)-C(3)-N(1) 112.4(13) C(38)-C(40) 1.504(18) C(29)-C(30)-C(31) 117.4(15) C(12)-C(13A) 1.55(5) C(29)-C(30)-C(38) 120.8(12) C(12)-C(11A) 1.57(5) C(31)-C(30)-C(38) 121.7(15) C(13)-C(12A) 1.20(8) C(32)-C(31)-C(30) 120.5(17) C(13)-C(13A) 1.72(8) C(12A)-C(10)-C(11A) 120(3) C(11A)-C(11) 1.53(5) C(12A)-C(10)-C(2) 104.9(18)

262

C(11)-C(12A) 1.65(6) C(11A)-C(10)-C(2) 94.4(15) C(51)-C(50) 1.19(4) C(12A)-C(10)-C(13A) 112(3) C(51)-C(52) #1 1.66(6) C(11A)-C(10)-C(13A) 121(3) C(50)-C(52) 1.32(6) C(2)-C(10)-C(13A) 98.5(19) C(52)-C(50) #1 1.32(6) C(12A)-C(10)-C(12) 136(2) C(11A)-C(10)-C(12) 62(2) C(2)-C(10)-C(12) 119.0(18) C(13A)-C(10)-C(12) 61(2) C(12A)-C(10)-C(13) 46(3) C(11A)-C(10)-C(13) 146(2) C(2)-C(10)-C(13) 117.8(14) C(13A)-C(10)-C(13) 67(3) C(12)-C(10)-C(13) 105(3) C(12A)-C(10)-C(11) 63(3) C(11A)-C(10)-C(11) 56.7(19) C(2)-C(10)-C(11) 114.2(14) C(13A)-C(10)-C(11) 147(2) C(12)-C(10)-C(11) 98.5(15) C(13)-C(10)-C(11) 99(3) C(36)-C(35)-C(37) 110.0(16) C(36)-C(35)-C(34) 114.8(18) C(37)-C(35)-C(34) 109(3) C(31)-C(32)-C(33) 121.2(13) C(32)-C(33)-C(34) 121.1(17) C(30)-C(38)-C(39) 113.0(19) C(30)-C(38)-C(40) 113(2) C(39)-C(38)-C(40) 107.2(17) C(13A)-C(12)-C(10) 57.7(17) C(13A)-C(12)-C(11A) 111.9(19) C(10)-C(12)-C(11A) 56.4(14) C(12A)-C(13)-C(10) 57.6(19) C(12A)-C(13)-C(13A) 111(3) C(10)-C(13)-C(13A) 54(2) C(10)-C(13A)-C(12) 61.4(16) C(10)-C(13A)-C(13) 60(2) C(12)-C(13A)-C(13) 101(2) C(10)-C(11A)-C(11) 69(2) C(10)-C(11A)-C(12) 61.5(19) C(11)-C(11A)-C(12) 106(3) C(11A)-C(11)-C(12A) 103(2) C(11A)-C(11)-C(10) 54.1(14) C(12A)-C(11)-C(10) 49.3(15) C(13)-C(12A)-C(10) 76(4) C(13)-C(12A)-C(11) 123(4)

263

C(10)-C(12A)-C(11) 67(2) C(50)-C(51)-C(52) 128(3) C(51)-C(50)-C(52) 138(6) C(50)#1-C(52)-C(51) 94(4)

264

12. X-Ray crystallographic data for [(SIPr)Au(1-benzyl-4-ferrocenyltriazolato)]

Table AI-12a. Crystallographic data for Table AI-12b. Data collection

ND120508

C46H54AuFeN5·C5H12 Bruker SMART CCD area-detector

Mr = 1001.90 diffractometer

Monoclinic, P21/c  scans

a = 11.014(4) Å Absorption correction: multi-scan

b = 30.374(10) Å Tmin = 0.2832, Tmax = 0.6243

c = 14.790(5) Å 39473 measured reflections

α = 90.00 º 10083 independent reflections

 = 110.532(4) º 8276 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0585

3 V = 4634(3) Å  max = 27.50º

Z = 4 h = -14  14

-3 Dx = 1.372 Mg m k = -39  39

Mo K radiation l = -19  19

Cell parameters from 9051 reflections

 = 1.34±27.50º

 = 3.515 mm-1

T = 100 (2) K

Irregular, orange

0.48  0.35 0.15 mm

265

Table AI-12c. Refinement Figure AI-12a. ORTEP plot of title

compound. Ellipsoids are at the 50%

probability level. The labels of H atoms are

omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0388 wR(F2) = 0.1011

S = 0.912

10083 reflections

533 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.1000P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.223

-3 max = 1.852 eÅ

-3 min = -2.956 eÅ

Table AI-12d. Selected geometric parameters (Å, º). Au(1)-C(20) 2.022(4) C(20)-Au(1)-C(1) 178.79(17) Au(1)-C(1) 2.023(4) C(8)-Fe(1)-C(7) 121.9(2) Fe(1)-C(8) 2.024(5) C(8)-Fe(1)-C(9) 40.3(2) Fe(1)-C(7) 2.033(4) C(7)-Fe(1)-C(9) 159.4(2) Fe(1)-C(9) 2.034(4) C(8)-Fe(1)-C(12) 40.8(2) Fe(1)-C(12) 2.036(5) C(7)-Fe(1)-C(12) 105.2(2) Fe(1)-C(6) 2.039(5) C(9)-Fe(1)-C(12) 68.0(2) Fe(1)-C(11) 2.042(6) C(8)-Fe(1)-C(6) 159.2(2) Fe(1)-C(10) 2.045(5) C(7)-Fe(1)-C(6) 40.96(19) Fe(1)-C(4) 2.048(5) C(9)-Fe(1)-C(6) 159.0(2) Fe(1)-C(5) 2.052(5) C(12)-Fe(1)-C(6) 123.0(2) Fe(1)-C(3) 2.064(5) C(8)-Fe(1)-C(11) 68.6(2) N(1)-N(2) 1.316(6) C(7)-Fe(1)-C(11) 120.1(2) N(1)-C(2) 1.367(5) C(9)-Fe(1)-C(11) 68.2(2) N(2)-N(3) 1.355(4) C(12)-Fe(1)-C(11) 40.5(2)

266

N(3)-C(1) 1.358(6) C(6)-Fe(1)-C(11) 107.5(2) N(3)-C(13) 1.453(6) C(8)-Fe(1)-C(10) 68.0(2) N(4)-C(20) 1.323(6) C(7)-Fe(1)-C(10) 157.3(2) N(4)-C(23) 1.438(6) C(9)-Fe(1)-C(10) 40.2(2) N(4)-C(21) 1.480(5) C(12)-Fe(1)-C(10) 68.1(2) N(5)-C(20) 1.334(5) C(6)-Fe(1)-C(10) 123.2(2) N(5)-C(35) 1.430(6) C(11)-Fe(1)-C(10) 40.8(2) N(5)-C(22) 1.475(5) C(8)-Fe(1)-C(4) 121.4(2) C(1)-C(2) 1.397(6) C(7)-Fe(1)-C(4) 68.96(19) C(23)-C(28) 1.402(6) C(9)-Fe(1)-C(4) 109.0(2) C(23)-C(24) 1.412(6) C(12)-Fe(1)-C(4) 156.2(2) C(29)-C(31) 1.514(8) C(6)-Fe(1)-C(4) 68.5(2) C(29)-C(24) 1.518(7) C(11)-Fe(1)-C(4) 162.4(2) C(29)-C(30) 1.527(7) C(10)-Fe(1)-C(4) 125.9(2) C(13)-C(14) 1.520(7) C(8)-Fe(1)-C(5) 157.7(2) C(2)-C(3) 1.440(6) C(7)-Fe(1)-C(5) 68.8(2) C(5)-C(4) 1.410(7) C(9)-Fe(1)-C(5) 123.8(2) C(5)-C(6) 1.428(7) C(12)-Fe(1)-C(5) 161.0(2) C(24)-C(25) 1.398(7) C(6)-Fe(1)-C(5) 40.8(2) C(9)-C(8) 1.399(7) C(11)-Fe(1)-C(5) 125.7(2) C(9)-C(10) 1.400(7) C(10)-Fe(1)-C(5) 110.2(2) C(6)-C(7) 1.425(7) C(4)-Fe(1)-C(5) 40.2(2) C(8)-C(12) 1.417(7) C(8)-Fe(1)-C(3) 105.6(2) C(22)-C(21) 1.526(6) C(7)-Fe(1)-C(3) 41.08(17) C(27)-C(28) 1.393(6) C(9)-Fe(1)-C(3) 123.87(19) C(27)-C(26) 1.396(7) C(12)-Fe(1)-C(3) 119.4(2) C(26)-C(25) 1.381(7) C(6)-Fe(1)-C(3) 68.92(19) C(12)-C(11) 1.412(8) C(11)-Fe(1)-C(3) 155.2(2) C(28)-C(32) 1.508(6) C(10)-Fe(1)-C(3) 161.31(19) C(3)-C(7) 1.438(6) C(4)-Fe(1)-C(3) 41.10(17) C(3)-C(4) 1.444(6) C(5)-Fe(1)-C(3) 68.57(19) C(14)-C(19) 1.383(6) N(2)-N(1)-C(2) 109.1(3) C(14)-C(15) 1.386(7) N(1)-N(2)-N(3) 106.0(3) C(18)-C(17) 1.373(8) N(2)-N(3)-C(1) 113.5(4) C(18)-C(19) 1.385(8) N(2)-N(3)-C(13) 118.1(3) C(15)-C(16) 1.385(8) C(1)-N(3)-C(13) 128.0(3) C(11)-C(10) 1.424(7) C(20)-N(4)-C(23) 125.4(3) C(16)-C(17) 1.391(7) C(20)-N(4)-C(21) 113.6(4) C(38)-C(37) 1.382(7) C(23)-N(4)-C(21) 119.8(3) C(38)-C(39) 1.381(9) C(20)-N(5)-C(35) 128.1(3) C(39)-C(40) 1.398(8) C(20)-N(5)-C(22) 112.9(4) C(35)-C(36) 1.383(7) C(35)-N(5)-C(22) 118.9(3) C(35)-C(40) 1.405(6) N(3)-C(1)-C(2) 101.7(4) C(36)-C(37) 1.401(7) N(3)-C(1)-Au(1) 123.6(3)

267

C(36)-C(41) 1.524(7) C(2)-C(1)-Au(1) 134.5(3) C(42)-C(41) 1.521(7) N(4)-C(20)-N(5) 108.7(3) C(41)-C(43) 1.520(7) N(4)-C(20)-Au(1) 126.3(3) C(40)-C(44) 1.527(8) N(5)-C(20)-Au(1) 125.0(3) C(44)-C(46) 1.506(8) C(28)-C(23)-C(24) 122.9(4) C(44)-C(45) 1.528(7) C(28)-C(23)-N(4) 119.0(4) C(32)-C(33) 1.526(6) C(24)-C(23)-N(4) 118.0(4) C(32)-C(34) 1.545(6) C(31)-C(29)-C(24) 112.3(5) C(49)-C(50) 1.436(12) C(31)-C(29)-C(30) 110.3(5) C(49)-C(48) 1.472(12) C(24)-C(29)-C(30) 111.0(4) C(48)-C(47) 1.544(13) N(3)-C(13)-C(14) 112.5(4) C(50)-C(51) 1.546(14) N(1)-C(2)-C(1) 109.7(4) N(1)-C(2)-C(3) 120.7(4) C(1)-C(2)-C(3) 129.5(4) C(4)-C(5)-C(6) 108.3(4) C(4)-C(5)-Fe(1) 69.7(3) C(6)-C(5)-Fe(1) 69.1(3) C(25)-C(24)-C(23) 117.7(4) C(25)-C(24)-C(29) 119.7(5) C(23)-C(24)-C(29) 122.6(4) C(8)-C(9)-C(10) 108.8(4) C(8)-C(9)-Fe(1) 69.4(3) C(10)-C(9)-Fe(1) 70.3(3) C(7)-C(6)-C(5) 107.9(4) C(7)-C(6)-Fe(1) 69.3(3) C(5)-C(6)-Fe(1) 70.1(3) C(7)-C(6)-H(6) 126.0 C(9)-C(8)-C(12) 107.8(5) C(9)-C(8)-Fe(1) 70.2(3) C(12)-C(8)-Fe(1) 70.0(3) N(5)-C(22)-C(21) 102.8(3) C(28)-C(27)-C(26) 121.9(5) C(25)-C(26)-C(27) 120.0(5) N(4)-C(21)-C(22) 102.0(3) C(11)-C(12)-C(8) 108.2(4) C(11)-C(12)-Fe(1) 70.0(3) C(8)-C(12)-Fe(1) 69.1(3) C(27)-C(28)-C(23) 116.7(4) C(27)-C(28)-C(32) 120.9(4) C(23)-C(28)-C(32) 122.3(4) C(7)-C(3)-C(2) 127.6(4) C(7)-C(3)-C(4) 106.6(4) C(2)-C(3)-C(4) 125.8(4) C(7)-C(3)-Fe(1) 68.3(3)

268

C(2)-C(3)-Fe(1) 127.6(3) C(4)-C(3)-Fe(1) 68.8(3) C(19)-C(14)-C(15) 119.0(5) C(19)-C(14)-C(13) 118.8(4) C(15)-C(14)-C(13) 122.1(4) C(17)-C(18)-C(19) 120.7(5) C(26)-C(25)-C(24) 120.8(5) C(5)-C(4)-C(3) 108.7(4) C(5)-C(4)-Fe(1) 70.1(3) C(3)-C(4)-Fe(1) 70.0(3) C(16)-C(15)-C(14) 120.2(5) C(6)-C(7)-C(3) 108.4(4) C(6)-C(7)-Fe(1) 69.8(3) C(3)-C(7)-Fe(1) 70.6(2) C(12)-C(11)-C(10) 107.3(4) C(12)-C(11)-Fe(1) 69.5(3) C(10)-C(11)-Fe(1) 69.7(3) C(9)-C(10)-C(11) 107.9(5) C(9)-C(10)-Fe(1) 69.5(3) C(11)-C(10)-Fe(1) 69.5(3) C(15)-C(16)-C(17) 120.6(5) C(14)-C(19)-C(18) 120.6(5) C(37)-C(38)-C(39) 120.3(5) C(38)-C(39)-C(40) 120.9(5) C(36)-C(35)-C(40) 123.0(5) C(36)-C(35)-N(5) 118.8(4) C(40)-C(35)-N(5) 118.0(5) C(35)-C(36)-C(37) 117.5(5) C(35)-C(36)-C(41) 121.8(4) C(37)-C(36)-C(41) 120.7(5) C(38)-C(37)-C(36) 121.0(6) C(43)-C(41)-C(42) 112.2(5) C(43)-C(41)-C(36) 112.8(4) C(42)-C(41)-C(36) 109.5(4) C(39)-C(40)-C(35) 117.2(5) C(39)-C(40)-C(44) 120.0(5) C(35)-C(40)-C(44) 122.8(5) C(46)-C(44)-C(40) 112.8(5) C(46)-C(44)-C(45) 112.0(5) C(40)-C(44)-C(45) 110.7(5) C(28)-C(32)-C(33) 113.5(4) C(28)-C(32)-C(34) 109.1(3) C(33)-C(32)-C(34) 110.9(4) C(18)-C(17)-C(16) 118.9(5)

269

C(50)-C(49)-C(48) 113.0(7) C(49)-C(48)-C(47) 109.2(8) C(49)-C(50)-C(51) 114.8(8)

270

13. X-Ray crystallographic data for [(PPh3)Au(1-benzyl-4-carboxymethyltriazolato)]

Table AI-13a. Crystallographic data for Table AI-13b. Data collection

JU111408

C29H25AuN3O2P Bruker SMART CCD area-detector

Mr = 675.46 diffractometer

Monoclinic, P21/c  scans

a = 9.6041(7) Å Absorption correction: multi-scan

b = 14.4554(10) Å Tmin = 0.3606, Tmax = 0.5667

c = 18.4921(13) Å 30741 measured reflections

α = 90.00 º 6109 independent reflections

 = 91.0140(10)º 5504 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0271

3 V = 2566.9(3) Å  max = 27.97º

Z = 4 h = -12  12

-3 Dx = 1.372 Mg m k = -19  18

Mo K radiation l = -24 24

Cell parameters from 9858 reflections

 = 1.79±27.97º

 = 5.825 mm-1

T = 100 (2) K

Irregular, colorless

0.22  0.20 0.11 mm

271

Table AI-13c. Refinement Figure AI-13a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0162 wR(F2) = 0.0363

S = 1.027

6109 reflections

326 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0177P) + 1.1855P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.081

-3 max = 0.678 eÅ

-3 min = -0.413 eÅ

Table AI-13d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.033(2) C(1)-Au(1)-P(1) 171.56(6) Au(1)-P(1) 2.2762(5) C(24)-P(1)-C(18) 105.61(9) P(1)-C(24) 1.812(2) C(24)-P(1)-C(12) 106.68(9) P(1)-C(18) 1.814(2) C(18)-P(1)-C(12) 106.01(9) P(1)-C(12) 1.818(2) C(24)-P(1)-Au(1) 113.94(7) C(12)-C(13) 1.395(3) C(18)-P(1)-Au(1) 116.74(7) C(12)-C(17) 1.395(3) C(12)-P(1)-Au(1) 107.18(7) C(24)-C(25) 1.395(3) C(13)-C(12)-C(17) 119.05(18) C(24)-C(29) 1.397(3) C(13)-C(12)-P(1) 120.75(15) O(2)-C(3) 1.345(3) C(17)-C(12)-P(1) 119.67(15) O(2)-C(4) 1.447(3) C(25)-C(24)-C(29) 119.30(18) O(1)-C(3) 1.202(3) C(25)-C(24)-P(1) 122.47(16) C(21)-C(20) 1.381(3) C(29)-C(24)-P(1) 118.22(15) C(21)-C(22) 1.392(3) C(3)-O(2)-C(4) 115.35(18) C(13)-C(14) 1.386(3) C(20)-C(21)-C(22) 119.6(2) C(18)-C(23) 1.393(3) C(14)-C(13)-C(12) 120.38(19) C(18)-C(19) 1.395(3) C(23)-C(18)-C(19) 119.47(18)

272

C(23)-C(22) 1.382(3) C(23)-C(18)-P(1) 120.86(15) C(17)-C(16) 1.386(3) C(19)-C(18)-P(1) 119.66(15) C(20)-C(19) 1.389(3) C(22)-C(23)-C(18) 120.2(2) C(1)-N(1) 1.350(3) C(16)-C(17)-C(12) 120.34(19) C(1)-C(2) 1.392(3) C(21)-C(20)-C(19) 120.5(2) C(3)-C(2) 1.464(3) N(1)-C(1)-C(2) 101.56(17) C(5)-N(1) 1.457(3) N(1)-C(1)-Au(1) 127.64(15) C(5)-C(6) 1.507(3) C(2)-C(1)-Au(1) 130.78(16) C(25)-C(26) 1.386(3) O(1)-C(3)-O(2) 123.0(2) C(16)-C(15) 1.385(3) O(1)-C(3)-C(2) 125.0(2) C(29)-C(28) 1.387(3) O(2)-C(3)-C(2) 112.01(17) C(2)-N(3) 1.370(3) N(1)-C(5)-C(6) 113.27(17) N(3)-N(2) 1.306(3) C(26)-C(25)-C(24) 120.1(2) N(1)-N(2) 1.364(2) C(23)-C(22)-C(21) 120.3(2) C(11)-C(6) 1.387(3) C(15)-C(16)-C(17) 120.2(2) C(11)-C(10) 1.388(3) C(28)-C(29)-C(24) 119.8(2) C(26)-C(27) 1.378(3) N(3)-C(2)-C(1) 110.56(19) C(6)-C(7) 1.386(3) N(3)-C(2)-C(3) 120.24(18) C(15)-C(14) 1.386(3) C(1)-C(2)-C(3) 129.09(19) C(7)-C(8) 1.385(3) N(2)-N(3)-C(2) 108.04(17) C(28)-C(27) 1.386(3) C(1)-N(1)-N(2) 113.05(18) C(8)-C(9) 1.383(4) C(1)-N(1)-C(5) 128.02(18) C(10)-C(9) 1.382(3) N(2)-N(1)-C(5) 118.86(18) N(3)-N(2)-N(1) 106.78(17) C(6)-C(11)-C(10) 120.0(2) C(27)-C(26)-C(25) 120.6(2) C(7)-C(6)-C(11) 119.5(2) C(7)-C(6)-C(5) 119.0(2) C(11)-C(6)-C(5) 121.4(2) C(16)-C(15)-C(14) 120.0(2) C(8)-C(7)-C(6) 120.2(2) C(15)-C(14)-C(13) 120.1(2) C(27)-C(28)-C(29) 120.6(2) C(26)-C(27)-C(28) 119.6(2) C(9)-C(8)-C(7) 120.3(2) C(9)-C(10)-C(11) 120.4(2) C(10)-C(9)-C(8) 119.5(2) C(20)-C(19)-C(18) 119.9(2)

273

14. X-Ray crystallographic data for [(PPh3)Au(1-benzyl-4-phenyltriazolato)]

Table AI-14a. Crystallographic data for Table AI-14b. Data collection

ND110708

C33H27AuN3P Bruker SMART CCD area-detector

Mr = 693.51 diffractometer

Monoclinic, P21/n  scans

a = 17.073(2) Å Absorption correction: multi-scan

b = 9.1697(13) Å Tmin = 0.1979, Tmax = 0.4392

c = 17.541(2) Å 31466 measured reflections

α = 90.00 º 6359 independent reflections

 = 95.925(2)º 5747 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0368

3 V = 2731.4(7) Å  max = 27.75º

Z = 4 h = -22  22

-3 Dx = 1.372 Mg m k = -11  11

Mo K radiation l = -22 22

Cell parameters from 9632 reflections

 = 1.58±27.75º

 = 5.472 mm-1

T = 100 (2) K

Irregular, colorless

0.44  0.43 0.18 mm

274

Table AI-14c. Refinement Figure AI-14a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0286 wR(F2) = 0.1075

S = 0.984

6359 reflections

343 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.1000P) + 0.8501P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.128

-3 max = 3.343 eÅ

-3 min = -1.533 eÅ

Table AI-14d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.021(4) C(1)-Au(1)-P(1) 178.74(12) Au(1)-P(1) 2.2746(11) N(1)-C(1)-C(2) 101.2(4) C(1)-N(1) 1.358(5) N(1)-C(1)-Au(1) 125.2(3) C(1)-C(2) 1.397(6) C(2)-C(1)-Au(1) 133.5(3) C(9)-N(1) 1.467(5) N(1)-C(9)-C(10) 111.7(3) C(9)-C(10) 1.508(6) C(32)-C(33)-C(28) 120.5(5) C(33)-C(32) 1.395(6) C(23)-C(22)-C(27) 120.0(4) C(33)-C(28) 1.389(6) C(23)-C(22)-P(1) 121.7(3) C(22)-C(23) 1.392(6) C(27)-C(22)-P(1) 118.3(3) C(22)-C(27) 1.390(6) C(21)-C(16)-C(17) 119.1(3) C(22)-P(1) 1.809(4) C(21)-C(16)-P(1) 121.6(3) C(16)-C(21) 1.389(5) C(17)-C(16)-P(1) 119.3(3) C(16)-C(17) 1.404(5) C(18)-C(17)-C(16) 120.5(4) C(16)-P(1) 1.802(4) C(15)-C(10)-C(11) 119.8(4) C(17)-C(18) 1.378(5) C(15)-C(10)-C(9) 120.6(4) C(10)-C(15) 1.386(6) C(11)-C(10)-C(9) 119.7(4) C(10)-C(11) 1.398(6) C(20)-C(19)-C(18) 120.1(4) C(19)-C(20) 1.382(5) C(5)-C(6)-C(7) 119.3(4)

275

C(19)-C(18) 1.393(5) C(32)-C(31)-C(30) 120.0(4) C(6)-C(5) 1.383(8) C(17)-C(18)-C(19) 119.8(4) C(6)-C(7) 1.379(8) C(4)-C(3)-C(8) 117.6(4) C(31)-C(32) 1.384(7) C(4)-C(3)-C(2) 122.3(4) C(31)-C(30) 1.386(7) C(8)-C(3)-C(2) 120.1(4) C(3)-C(4) 1.400(6) C(29)-C(28)-C(33) 119.4(4) C(3)-C(8) 1.399(5) C(29)-C(28)-P(1) 122.6(3) C(3)-C(2) 1.469(5) C(33)-C(28)-P(1) 118.0(3) C(28)-C(29) 1.386(6) C(12)-C(13)-C(14) 120.6(5) C(28)-P(1) 1.815(4) C(26)-C(27)-C(22) 119.6(5) C(13)-C(12) 1.363(8) C(5)-C(4)-C(3) 120.9(4) C(13)-C(14) 1.394(8) C(19)-C(20)-C(21) 120.3(4) C(27)-C(26) 1.386(6) C(24)-C(23)-C(22) 119.4(4) C(4)-C(5) 1.386(6) C(20)-C(21)-C(16) 120.2(4) C(20)-C(21) 1.388(5) C(28)-C(29)-C(30) 120.2(4) C(23)-C(24) 1.385(6) C(31)-C(30)-C(29) 120.2(4) C(29)-C(30) 1.393(6) C(14)-C(15)-C(10) 120.2(5) C(15)-C(14) 1.383(7) C(25)-C(24)-C(23) 120.6(5) C(24)-C(25) 1.372(8) C(8)-C(7)-C(6) 120.8(5) C(7)-C(8) 1.373(6) C(24)-C(25)-C(26) 120.1(5) C(25)-C(26) 1.380(8) C(31)-C(32)-C(33) 119.7(4) C(12)-C(11) 1.392(7) C(13)-C(12)-C(11) 120.3(5) N(3)-N(2) 1.312(5) C(12)-C(11)-C(10) 119.5(5) N(3)-C(2) 1.370(5) C(7)-C(8)-C(3) 121.2(4) N(1)-N(2) 1.347(5) C(27)-C(26)-C(25) 120.2(5) C(6)-C(5)-C(4) 120.3(5) C(15)-C(14)-C(13) 119.6(5) C(22)-P(1)-C(16) 107.16(18) C(22)-P(1)-C(28) 105.68(19) C(16)-P(1)-C(28) 104.14(17) C(22)-P(1)-Au(1) 113.70(13) C(16)-P(1)-Au(1) 111.50(13) C(28)-P(1)-Au(1) 113.94(13) N(2)-N(3)-C(2) 108.3(3) N(2)-N(1)-C(1) 113.6(3) N(2)-N(1)-C(9) 119.0(3) C(1)-N(1)-C(9) 127.4(3) N(3)-N(2)-N(1) 106.7(3) N(3)-C(2)-C(1) 110.2(4) N(3)-C(2)-C(3) 119.3(3) C(1)-C(2)-C(3) 130.5(4)

276

15. X-Ray crystallographic data for [(PPh3)Au(1-benzyl-(4-tolyl)triazolato)]

Table AI-15a. Crystallographic data for Table AI-15b. Data collection

ND111108

C34H29AuN3P·C6H6 Bruker SMART CCD area-detector

Mr = 746.59 diffractometer

Monoclinic, C2/c  scans

a = 24.504(4) Å Absorption correction: multi-scan

b = 8.8512(14) Å Tmin = 0.2126, Tmax = 0.6335

c = 28.802(4) Å 35642 measured reflections

α = 90.00 º 7047 independent reflections

 = 100.730(2)º 6663 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0368

3 V = 6137.7(17) Å  max = 27.49º

Z = 8 h = -31  31

-3 Dx = 1.616 Mg m k = -11  11

Mo K radiation l = -37 37

Cell parameters from 9812 reflections

 = 1.44±27.49º

 = 4.877 mm-1

T = 100 (2) K

Irregular, colorless

0.46  0.31 0.10 mm

277

Table AI-15c. Refinement Figure AI-15a. ORTEP plot of title

compound. Ellipsoids are at the 50%

probability level. The labels of H atoms and

solvent molecules are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0167 wR(F2) = 0.0389

S = 1.071

7047 reflections

380 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0094P) + 11.9995P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.073

-3 max = 0.999 eÅ

-3 min = -0.987 eÅ

Table AI-15d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.034(2) C(1)-Au(1)-P(1) 178.25(6) Au(1)-P(1) 2.2797(6) C(17)-P(1)-C(29) 107.69(9) P(1)-C(17) 1.814(2) C(17)-P(1)-C(23) 103.18(9) P(1)-C(29) 1.816(2) C(29)-P(1)-C(23) 105.05(9) P(1)-C(23) 1.8161(19) C(17)-P(1)-Au(1) 112.93(7) C(11)-C(16) 1.385(3) C(29)-P(1)-Au(1) 112.83(6) C(11)-C(12) 1.391(3) C(23)-P(1)-Au(1) 114.36(6) C(11)-C(10) 1.506(3) C(16)-C(11)-C(12) 119.0(2) C(17)-C(22) 1.391(3) C(16)-C(11)-C(10) 121.1(2) C(17)-C(18) 1.396(3) C(12)-C(11)-C(10) 119.88(19) C(34)-C(33) 1.391(3) C(22)-C(17)-C(18) 119.55(19) C(34)-C(29) 1.397(3) C(22)-C(17)-P(1) 123.18(16) C(29)-C(30) 1.399(3) C(18)-C(17)-P(1) 117.27(15) C(4)-C(5) 1.392(3) C(33)-C(34)-C(29) 120.33(18) C(4)-C(3) 1.395(3) C(34)-C(29)-C(30) 119.01(18) C(23)-C(28) 1.390(3) C(34)-C(29)-P(1) 118.50(15) C(23)-C(24) 1.397(3) C(30)-C(29)-P(1) 122.43(15)

278

C(5)-C(6) 1.395(3) C(5)-C(4)-C(3) 121.22(19) C(30)-C(31) 1.386(3) C(28)-C(23)-C(24) 119.37(18) C(12)-C(13) 1.386(3) C(28)-C(23)-P(1) 119.01(15) C(24)-C(25) 1.389(3) C(24)-C(23)-P(1) 121.60(15) C(7)-C(8) 1.384(3) C(4)-C(5)-C(6) 121.2(2) C(7)-C(6) 1.389(3) C(31)-C(30)-C(29) 120.51(18) C(2)-N(1) 1.372(2) C(13)-C(12)-C(11) 120.4(2) C(2)-C(1) 1.393(3) C(25)-C(24)-C(23) 119.9(2) C(2)-C(3) 1.466(3) C(8)-C(7)-C(6) 121.54(19) C(28)-C(27) 1.388(3) N(1)-C(2)-C(1) 109.33(18) C(33)-C(32) 1.384(3) N(1)-C(2)-C(3) 119.31(17) C(21)-C(20) 1.377(3) C(1)-C(2)-C(3) 131.33(18) C(21)-C(22) 1.393(3) C(27)-C(28)-C(23) 120.35(19) C(31)-C(32) 1.389(3) C(32)-C(33)-C(34) 119.98(19) C(8)-C(3) 1.404(3) C(20)-C(21)-C(22) 120.7(2) C(10)-N(3) 1.462(3) C(30)-C(31)-C(32) 119.84(18) C(26)-C(27) 1.380(3) C(7)-C(8)-C(3) 121.2(2) C(26)-C(25) 1.385(3) N(3)-C(10)-C(11) 112.11(17) C(6)-C(9) 1.514(3) C(27)-C(26)-C(25) 120.1(2) C(20)-C(19) 1.388(3) C(26)-C(27)-C(28) 120.1(2) C(18)-C(19) 1.386(3) C(7)-C(6)-C(5) 117.6(2) C(36)-C(37) 1.385(3) C(7)-C(6)-C(9) 120.74(19) C(36)-C(35) 1.384(3) C(5)-C(6)-C(9) 121.7(2) C(37)-C(35)#1 1.378(3) C(21)-C(20)-C(19) 119.9(2) C(14)-C(15) 1.381(4) C(17)-C(22)-C(21) 119.7(2) C(14)-C(13) 1.384(4) C(19)-C(18)-C(17) 120.2(2) C(16)-C(15) 1.390(3) C(26)-C(25)-C(24) 120.2(2) C(35)-C(37)#1 1.378(3) C(37)-C(36)-C(35) 119.7(2) N(2)-N(1) 1.310(3) C(35)#1-C(37)-C(36) 120.3(2) N(2)-N(3) 1.352(2) C(33)-C(32)-C(31) 120.34(19) N(3)-C(1) 1.359(3) C(15)-C(14)-C(13) 119.9(2) C(11)-C(16)-C(15) 120.6(2) C(18)-C(19)-C(20) 120.1(2) C(37)#1-C(35)-C(36) 120.0(2) C(14)-C(15)-C(16) 119.9(2) C(14)-C(13)-C(12) 120.1(2) N(1)-N(2)-N(3) 106.50(16) N(2)-N(1)-C(2) 109.00(17) N(2)-N(3)-C(1) 113.02(17) N(2)-N(3)-C(10) 118.47(17) C(1)-N(3)-C(10) 128.45(17) C(4)-C(3)-C(8) 117.2(2) C(4)-C(3)-C(2) 122.53(18) C(8)-C(3)-C(2) 120.14(19)

279

N(3)-C(1)-C(2) 102.15(17) N(3)-C(1)-Au(1) 122.15(15) C(2)-C(1)-Au(1) 135.65(15)

280

16. X-Ray crystallographic data for [(PPh3)Au(1-benzyl-(4-fluorophenyl)triazolato)]

Table AI-16a. Crystallographic data for Table AI-16b. Data collection

ND121008

C33H26AuFN3P Bruker SMART CCD area-detector

Mr = 711.50 diffractometer

Monoclinic, P21/c  scans

a = 10.6315(13) Å Absorption correction: multi-scan

b = 16.827(2) Å Tmin = 0.2351, Tmax = 0.4730

c = 15.2109(18) Å 27379 measured reflections

α = 90.00 º 5721 independent reflections

 = 102.9620(10)º 5190 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0457

3 V = 2651.8(6) Å  max = 27.11º

Z = 4 h = -13  13

-3 Dx = 1.782 Mg m k = -21  21

Mo K radiation l = -19 19

Cell parameters from 9437 reflections

 = 1.83±27.11º

 = 5.644 mm-1

T = 100 (2) K

Irregular, colorless

0.36  0.18 0.16 mm

281

Table AI-16c. Refinement Figure AI-16a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0399 wR(F2) = 0.1265

S = 1.086

5721 reflections

352 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.1000P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.232

-3 max = 1.152 eÅ

-3 min = -2.094 eÅ

Table AI-16d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.028(4) C(1)-Au(1)-P(1) 177.59(13) Au(1)-P(1) 2.2720(12) C(16)-P(1)-C(22) 103.8(2) P(1)-C(16) 1.806(5) C(16)-P(1)-C(28) 104.6(2) P(1)-C(22) 1.806(4) C(22)-P(1)-C(28) 106.6(2) P(1)-C(28) 1.811(4) C(16)-P(1)-Au(1) 111.27(15) C(1)-N(1) 1.347(6) C(22)-P(1)-Au(1) 113.55(15) C(1)-C(2) 1.389(6) C(28)-P(1)-Au(1) 115.91(15) C(19)-C(18) 1.376(8) N(1)-C(1)-C(2) 101.9(4) C(19)-C(20) 1.382(7) N(1)-C(1)-Au(1) 123.4(3) C(15)-C(10) 1.380(7) C(2)-C(1)-Au(1) 134.5(3) C(15)-C(14) 1.395(7) C(18)-C(19)-C(20) 120.4(4) C(6)-F(1) 1.357(5) C(10)-C(15)-C(14) 120.3(5) C(6)-C(5) 1.366(7) F(1)-C(6)-C(5) 119.1(4) C(6)-C(7) 1.375(7) F(1)-C(6)-C(7) 118.0(4) C(10)-C(11) 1.391(6) C(5)-C(6)-C(7) 122.9(5) C(10)-C(9) 1.518(6) C(15)-C(10)-C(11) 119.4(4) C(22)-C(23) 1.383(7) C(15)-C(10)-C(9) 121.2(4) C(22)-C(27) 1.399(6) C(11)-C(10)-C(9) 119.2(4)

282

C(23)-C(24) 1.389(7) C(23)-C(22)-C(27) 119.1(4) C(18)-C(17) 1.379(7) C(23)-C(22)-P(1) 117.7(4) C(25)-C(26) 1.369(6) C(27)-C(22)-P(1) 123.1(3) C(25)-C(24) 1.388(6) C(22)-C(23)-C(24) 120.5(4) C(14)-C(13) 1.376(7) C(19)-C(18)-C(17) 119.8(4) C(4)-C(3) 1.386(6) C(26)-C(25)-C(24) 119.9(4) C(4)-C(5) 1.391(7) C(13)-C(14)-C(15) 119.3(5) C(8)-C(3) 1.382(7) C(25)-C(24)-C(23) 119.8(4) C(8)-C(7) 1.394(7) C(3)-C(4)-C(5) 121.1(4) C(17)-C(16) 1.401(6) C(3)-C(8)-C(7) 121.6(4) C(27)-C(26) 1.386(6) C(18)-C(17)-C(16) 120.6(4) C(32)-C(31) 1.381(7) C(26)-C(27)-C(22) 119.8(4) C(32)-C(33) 1.387(7) C(31)-C(32)-C(33) 120.3(5) C(33)-C(28) 1.387(6) C(25)-C(26)-C(27) 120.7(4) C(13)-C(12) 1.380(7) C(28)-C(33)-C(32) 120.1(4) C(21)-C(16) 1.384(6) C(14)-C(13)-C(12) 121.0(5) C(21)-C(20) 1.390(7) C(16)-C(21)-C(20) 119.9(4) C(29)-C(30) 1.373(6) C(30)-C(29)-C(28) 119.5(4) C(29)-C(28) 1.404(6) C(21)-C(16)-C(17) 119.1(4) C(30)-C(31) 1.397(7) C(21)-C(16)-P(1) 121.5(3) C(11)-C(12) 1.380(7) C(17)-C(16)-P(1) 119.3(3) C(2)-N(3) 1.363(6) C(33)-C(28)-C(29) 119.8(4) C(2)-C(3) 1.474(6) C(33)-C(28)-P(1) 119.8(4) N(1)-N(2) 1.364(6) C(29)-C(28)-P(1) 120.4(3) N(1)-C(9) 1.437(5) C(29)-C(30)-C(31) 120.7(4) N(3)-N(2) 1.307(5) C(12)-C(11)-C(10) 120.4(4) C(6)-C(5)-C(4) 118.3(4) N(3)-C(2)-C(1) 110.1(4) N(3)-C(2)-C(3) 120.5(4) C(1)-C(2)-C(3) 129.4(4) C(8)-C(3)-C(4) 118.5(4) C(8)-C(3)-C(2) 120.6(4) C(4)-C(3)-C(2) 120.9(4) C(6)-C(7)-C(8) 117.6(5) C(19)-C(20)-C(21) 120.2(5) C(13)-C(12)-C(11) 119.5(4) C(1)-N(1)-N(2) 113.0(3) C(1)-N(1)-C(9) 128.0(4) N(2)-N(1)-C(9) 118.9(4) N(2)-N(3)-C(2) 108.7(4) N(3)-N(2)-N(1) 106.2(4) C(32)-C(31)-C(30) 119.6(4) N(1)-C(9)-C(10) 114.2(4)

283

17. X-Ray crystallographic data for [(PPh3)Au(1-benzyl-(4-ferrocenyl)triazolato)]

Table AI-17a. Crystallographic data for Table AI-17b. Data collection

JU111908

C37H31AuFeN3P Bruker SMART CCD area-detector

Mr = 801.43 diffractometer

Monoclinic, P21/c  scans

a = 23.71(2) Å Absorption correction: multi-scan

b = 9.026(9)Å Tmin = 0.2664, Tmax = 0.6275

c = 29.77(3) Å 54027 measured reflections

α = 90.00 º 14504 independent reflections

 = 91.702(10)º 12999 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0357

3 V = 6368(10) Å  max = 27.50º

Z = 8 h = -30  30

-3 Dx = 1.672 Mg m k = -11  11

Mo K radiation l = -38  38

Cell parameters from 9178 reflections

 = 0.86±27.50º

 = 5.138 mm-1

T = 100 (2) K

Irregular, colorless

0.35  0.32 0.10 mm

284

Table AI-17c. Refinement Figure AI-17a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0216 wR(F2) = 0.0481

S = 1.074

14504 reflections

775 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0182P) + 9.6053P]

2 2 where P = (Fo + 2Fc )/3

(/) = 0.098 max -3 max = 1.759 eÅ

-3 min = -1.573 eÅ

Table AI-17d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.050(3) C(1)-Au(1)-P(1) 176.00(8) Au(1)-P(1) 2.307(2) C(12)-Fe(1)-C(8) 41.29(16) Fe(1)-C(12) 2.043(4) C(12)-Fe(1)-C(7) 106.31(15) Fe(1)-C(8) 2.050(4) C(8)-Fe(1)-C(7) 115.85(14) Fe(1)-C(7) 2.064(3) C(12)-Fe(1)-C(6) 116.76(16) Fe(1)-C(6) 2.064(3) C(8)-Fe(1)-C(6) 149.85(15) Fe(1)-C(4) 2.069(3) C(7)-Fe(1)-C(6) 40.68(13) Fe(1)-C(3) 2.069(3) C(12)-Fe(1)-C(4) 165.46(15) Fe(1)-C(5) 2.069(3) C(8)-Fe(1)-C(4) 127.47(13) Fe(1)-C(9) 2.070(3) C(7)-Fe(1)-C(4) 68.45(13) Fe(1)-C(11) 2.069(4) C(6)-Fe(1)-C(4) 68.76(12) Fe(1)-C(10) 2.079(3) C(12)-Fe(1)-C(3) 126.56(15) P(1)-C(32) 1.827(3) C(8)-Fe(1)-C(3) 105.62(12) P(1)-C(20) 1.837(3) C(7)-Fe(1)-C(3) 41.07(11) P(1)-C(26) 1.838(3) C(6)-Fe(1)-C(3) 69.13(11) Au(2)-C(38) 2.054(3) C(4)-Fe(1)-C(3) 40.75(12) Au(2)-P(2) 2.299(2) C(12)-Fe(1)-C(5) 151.42(15) P(2)-C(63) 1.832(3) C(8)-Fe(1)-C(5) 166.92(14)

285

P(2)-C(57) 1.834(3) C(7)-Fe(1)-C(5) 68.38(13) P(2)-C(69) 1.838(3) C(6)-Fe(1)-C(5) 40.79(13) C(13)-N(1) 1.474(4) C(4)-Fe(1)-C(5) 40.86(11) C(13)-C(14) 1.525(4) C(3)-Fe(1)-C(5) 68.89(11) C(27)-C(28) 1.406(4) C(12)-Fe(1)-C(9) 68.26(16) C(27)-C(26) 1.416(4) C(8)-Fe(1)-C(9) 40.35(15) C(20)-C(21) 1.398(4) C(7)-Fe(1)-C(9) 149.98(13) C(20)-C(25) 1.405(4) C(6)-Fe(1)-C(9) 168.63(14) C(63)-C(64) 1.413(4) C(4)-Fe(1)-C(9) 109.04(13) C(63)-C(68) 1.413(4) C(3)-Fe(1)-C(9) 117.02(12) N(4)-C(38) 1.361(4) C(5)-Fe(1)-C(9) 130.43(14) N(4)-N(5) 1.370(4) C(12)-Fe(1)-C(11) 40.65(16) N(4)-C(50) 1.491(5) C(8)-Fe(1)-C(11) 68.73(14) C(32)-C(33) 1.401(4) C(7)-Fe(1)-C(11) 128.17(14) C(32)-C(37) 1.418(4) C(6)-Fe(1)-C(11) 108.66(13) C(61)-C(62) 1.403(4) C(4)-Fe(1)-C(11) 152.97(14) C(61)-C(60) 1.407(5) C(3)-Fe(1)-C(11) 165.58(14) C(26)-C(31) 1.413(4) C(5)-Fe(1)-C(11) 119.40(14) C(68)-C(67) 1.404(4) C(9)-Fe(1)-C(11) 67.89(14) C(68)-H(68) 0.9500 C(12)-Fe(1)-C(10) 67.55(16) C(38)-C(39) 1.413(4) C(8)-Fe(1)-C(10) 67.74(14) C(57)-C(62) 1.402(4) C(7)-Fe(1)-C(10) 167.01(13) C(57)-C(58) 1.411(4) C(6)-Fe(1)-C(10) 130.51(14) C(71)-C(72) 1.397(4) C(4)-Fe(1)-C(10) 120.29(15) C(71)-C(70) 1.407(4) C(3)-Fe(1)-C(10) 151.77(13) N(5)-N(6) 1.330(4) C(5)-Fe(1)-C(10) 111.12(14) C(6)-C(7) 1.435(5) C(9)-Fe(1)-C(10) 40.11(13) C(6)-C(5) 1.440(5) C(11)-Fe(1)-C(10) 39.88(15) C(4)-C(5) 1.444(4) C(32)-P(1)-C(20) 105.17(14) C(4)-C(3) 1.441(4) C(32)-P(1)-C(26) 106.34(13) C(21)-C(22) 1.410(4) C(20)-P(1)-C(26) 104.35(13) C(31)-C(30) 1.406(4) C(32)-P(1)-Au(1) 110.05(9) C(64)-C(65) 1.403(4) C(20)-P(1)-Au(1) 114.69(10) C(51)-C(52) 1.395(5) C(26)-P(1)-Au(1) 115.41(10) C(51)-C(56) 1.407(5) C(38)-Au(2)-P(2) 178.16(8) C(51)-C(50) 1.518(5) C(63)-P(2)-C(57) 104.97(13) C(14)-C(15) 1.392(4) C(63)-P(2)-C(69) 107.78(14) C(14)-C(19) 1.413(4) C(57)-P(2)-C(69) 104.63(14) C(66)-C(67) 1.398(5) C(63)-P(2)-Au(2) 110.13(11) C(66)-C(65) 1.402(5) C(57)-P(2)-Au(2) 114.50(9) C(24)-C(23) 1.389(5) C(69)-P(2)-Au(2) 114.18(10) C(24)-C(25) 1.406(4) N(1)-C(13)-C(14) 109.5(2) C(36)-C(37) 1.390(4) C(28)-C(27)-C(26) 120.2(3) C(36)-C(35) 1.394(5) C(21)-C(20)-C(25) 119.8(3)

286

C(10)-C(11) 1.414(5) C(21)-C(20)-P(1) 117.9(2) C(10)-C(9) 1.423(5) C(25)-C(20)-P(1) 122.2(2) N(6)-C(39) 1.373(4) C(64)-C(63)-C(68) 119.6(3) C(7)-C(3) 1.450(4) C(64)-C(63)-P(2) 116.5(2) C(74)-C(73) 1.405(4) C(68)-C(63)-P(2) 123.9(2) C(74)-C(69) 1.404(4) C(38)-N(4)-N(5) 112.3(3) C(55)-C(54) 1.383(6) C(38)-N(4)-C(50) 132.7(3) C(55)-C(56) 1.403(6) N(5)-N(4)-C(50) 114.9(3) C(3)-C(2) 1.476(4) C(33)-C(32)-C(37) 119.2(3) C(70)-C(69) 1.411(4) C(33)-C(32)-P(1) 123.0(2) C(52)-C(53) 1.402(5) C(37)-C(32)-P(1) 117.8(2) C(16)-C(17) 1.400(5) C(62)-C(61)-C(60) 120.6(3) C(16)-C(15) 1.403(4) C(31)-C(26)-C(27) 119.4(3) C(54)-C(53) 1.383(5) C(31)-C(26)-P(1) 118.3(2) C(73)-C(72) 1.401(5) C(27)-C(26)-P(1) 122.2(2) C(58)-C(59) 1.402(4) C(67)-C(68)-C(63) 119.9(3) C(35)-C(34) 1.401(5) N(4)-C(38)-C(39) 102.4(3) C(22)-C(23) 1.403(5) N(4)-C(38)-Au(2) 128.9(2) C(60)-C(59) 1.389(5) C(39)-C(38)-Au(2) 128.7(2) C(30)-C(29) 1.408(4) C(62)-C(57)-C(58) 119.2(3) C(33)-C(34) 1.393(4) C(62)-C(57)-P(2) 122.1(2) C(29)-C(28) 1.400(5) C(58)-C(57)-P(2) 118.6(2) C(9)-C(8) 1.421(5) C(72)-C(71)-C(70) 120.0(3) C(12)-C(11) 1.429(6) N(6)-N(5)-N(4) 107.3(2) C(12)-C(8) 1.443(6) C(7)-C(6)-C(5) 107.8(3) C(19)-C(18) 1.396(4) C(7)-C(6)-Fe(1) 69.68(17) C(18)-C(17) 1.389(5) C(5)-C(6)-Fe(1) 69.81(16) N(1)-N(2) 1.372(3) C(5)-C(4)-C(3) 108.4(3) N(1)-C(1) 1.370(4) C(5)-C(4)-Fe(1) 69.59(17) N(2)-N(3) 1.332(3) C(3)-C(4)-Fe(1) 69.63(16) N(3)-C(2) 1.377(4) C(20)-C(21)-C(22) 119.5(3) C(1)-C(2) 1.416(4) C(30)-C(31)-C(26) 120.0(3) C(43)-C(42) 1.431(5) C(65)-C(64)-C(63) 119.9(3) C(43)-C(44) 1.440(5) C(52)-C(51)-C(56) 118.3(3) C(43)-Fe(2) 2.054(4) C(52)-C(51)-C(50) 120.4(3) C(44)-C(40) 1.441(4) C(56)-C(51)-C(50) 121.2(3) C(44)-Fe(2) 2.071(4) C(15)-C(14)-C(19) 118.6(3) C(41)-C(42) 1.431(5) C(15)-C(14)-C(13) 120.5(3) C(41)-C(40) 1.443(5) C(19)-C(14)-C(13) 120.8(3) C(41)-Fe(2) 2.070(4) C(67)-C(66)-C(65) 120.1(3) C(40)-C(39) 1.480(5) C(23)-C(24)-C(25) 119.3(3) C(40)-Fe(2) 2.084(4) C(57)-C(62)-C(61) 119.7(3) C(48)-C(47) 1.371(6) C(37)-C(36)-C(35) 119.7(3) C(48)-C(49) 1.411(8) C(11)-C(10)-C(9) 109.1(3)

287

C(48)-Fe(2) 2.075(5) C(11)-C(10)-Fe(1) 69.7(2) C(42)-Fe(2) 2.068(4) C(9)-C(10)-Fe(1) 69.62(19) C(49)-C(45) 1.464(10) N(5)-N(6)-C(39) 108.0(2) C(49)-Fe(2) 2.049(5) C(6)-C(7)-C(3) 108.7(3) Fe(2)-C(46) 2.029(5) C(6)-C(7)-Fe(1) 69.64(18) Fe(2)-C(45) 2.041(5) C(3)-C(7)-Fe(1) 69.63(17) C(46)-C(47) 1.366(8) C(73)-C(74)-C(69) 120.2(3) C(46)-C(45) 1.370(11) C(54)-C(55)-C(56) 120.3(3) C(4)-C(3)-C(7) 107.1(3) C(4)-C(3)-C(2) 126.8(2) C(7)-C(3)-C(2) 126.0(3) C(4)-C(3)-Fe(1) 69.62(15) C(7)-C(3)-Fe(1) 69.30(17) C(2)-C(3)-Fe(1) 122.65(19) C(71)-C(70)-C(69) 120.7(3) C(51)-C(52)-C(53) 120.8(3) C(36)-C(37)-C(32) 120.7(3) C(6)-C(5)-C(4) 108.0(3) C(6)-C(5)-Fe(1) 69.40(17) C(4)-C(5)-Fe(1) 69.55(16) C(66)-C(65)-C(64) 120.2(3) C(17)-C(16)-C(15) 120.1(3) C(53)-C(54)-C(55) 119.8(3) C(74)-C(73)-C(72) 120.7(3) C(59)-C(58)-C(57) 120.8(3) C(14)-C(15)-C(16) 120.5(3) C(24)-C(25)-C(20) 120.7(3) C(36)-C(35)-C(34) 119.9(3) C(23)-C(22)-C(21) 120.3(3) C(54)-C(53)-C(52) 120.3(3) C(59)-C(60)-C(61) 119.9(3) C(74)-C(69)-C(70) 118.8(3) C(74)-C(69)-P(2) 118.2(2) C(70)-C(69)-P(2) 123.0(2) C(31)-C(30)-C(29) 120.2(3) C(34)-C(33)-C(32) 119.6(3) C(28)-C(29)-C(30) 120.1(3) C(8)-C(9)-C(10) 108.0(3) C(8)-C(9)-Fe(1) 69.08(19) C(10)-C(9)-Fe(1) 70.27(18) C(11)-C(12)-C(8) 108.1(3) C(11)-C(12)-Fe(1) 70.6(2) C(8)-C(12)-Fe(1) 69.6(2) C(60)-C(59)-C(58) 119.7(3)

288

C(9)-C(8)-C(12) 107.3(3) C(9)-C(8)-Fe(1) 70.56(17) C(12)-C(8)-Fe(1) 69.08(19) C(18)-C(19)-C(14) 121.1(3) C(10)-C(11)-C(12) 107.4(3) C(10)-C(11)-Fe(1) 70.42(19) C(12)-C(11)-Fe(1) 68.7(2) C(66)-C(67)-C(68) 120.2(3) C(33)-C(34)-C(35) 120.9(3) C(71)-C(72)-C(73) 119.5(3) C(17)-C(18)-C(19) 119.6(3) C(18)-C(17)-C(16) 120.1(3) C(24)-C(23)-C(22) 120.5(3) N(2)-N(1)-C(1) 113.1(2) N(2)-N(1)-C(13) 118.2(2) C(1)-N(1)-C(13) 128.0(2) N(3)-N(2)-N(1) 106.9(2) N(2)-N(3)-C(2) 108.1(2) N(1)-C(1)-C(2) 101.5(2) N(1)-C(1)-Au(1) 125.8(2) C(2)-C(1)-Au(1) 132.7(2) C(29)-C(28)-C(27) 120.1(3) N(3)-C(2)-C(1) 110.5(2) N(3)-C(2)-C(3) 120.7(2) C(1)-C(2)-C(3) 128.7(3) C(42)-C(43)-C(44) 108.5(3) C(42)-C(43)-Fe(2) 70.2(2) C(44)-C(43)-Fe(2) 70.22(19) C(43)-C(44)-C(40) 108.1(3) C(43)-C(44)-Fe(2) 68.9(2) C(40)-C(44)-Fe(2) 70.18(19) C(42)-C(41)-C(40) 109.1(3) C(42)-C(41)-Fe(2) 69.7(2) C(40)-C(41)-Fe(2) 70.2(2) C(55)-C(56)-C(51) 120.4(3) C(41)-C(40)-C(44) 106.9(3) C(41)-C(40)-C(39) 125.4(3) C(44)-C(40)-C(39) 127.7(3) C(41)-C(40)-Fe(2) 69.2(2) C(44)-C(40)-Fe(2) 69.24(19) C(39)-C(40)-Fe(2) 127.4(2) N(6)-C(39)-C(38) 110.0(3) N(6)-C(39)-C(40) 120.1(3) C(38)-C(39)-C(40) 129.9(3)

289

N(4)-C(50)-C(51) 117.3(3) C(47)-C(48)-C(49) 107.6(5) C(47)-C(48)-Fe(2) 69.9(3) C(49)-C(48)-Fe(2) 69.0(3) C(41)-C(42)-C(43) 107.4(3) C(41)-C(42)-Fe(2) 69.9(2) C(43)-C(42)-Fe(2) 69.2(2) C(48)-C(49)-C(45) 106.7(5) C(48)-C(49)-Fe(2) 71.0(3) C(45)-C(49)-Fe(2) 68.7(3) C(46)-Fe(2)-C(45) 39.3(3) C(46)-Fe(2)-C(49) 67.2(3) C(45)-Fe(2)-C(49) 42.0(3) C(46)-Fe(2)-C(43) 173.5(3) C(45)-Fe(2)-C(43) 146.9(3) C(49)-Fe(2)-C(43) 116.5(2) C(46)-Fe(2)-C(47) 39.0(2) C(45)-Fe(2)-C(47) 66.5(2) C(49)-Fe(2)-C(47) 66.3(2) C(43)-Fe(2)-C(47) 136.31(19) C(46)-Fe(2)-C(42) 133.2(3) C(45)-Fe(2)-C(42) 172.1(4) C(49)-Fe(2)-C(42) 143.6(3) C(43)-Fe(2)-C(42) 40.62(15) C(47)-Fe(2)-C(42) 109.2(2) C(46)-Fe(2)-C(41) 108.4(3) C(45)-Fe(2)-C(41) 133.7(3) C(49)-Fe(2)-C(41) 175.4(2) C(43)-Fe(2)-C(41) 68.02(15) C(47)-Fe(2)-C(41) 111.4(2) C(42)-Fe(2)-C(41) 40.46(15) C(46)-Fe(2)-C(44) 143.8(2) C(45)-Fe(2)-C(44) 116.0(2) C(49)-Fe(2)-C(44) 114.49(17) C(43)-Fe(2)-C(44) 40.85(13) C(47)-Fe(2)-C(44) 177.15(18) C(42)-Fe(2)-C(44) 68.51(16) C(41)-Fe(2)-C(44) 68.01(15) C(46)-Fe(2)-C(48) 66.07(19) C(45)-Fe(2)-C(48) 68.2(2) C(49)-Fe(2)-C(48) 40.0(2) C(43)-Fe(2)-C(48) 112.95(16) C(47)-Fe(2)-C(48) 38.76(18) C(42)-Fe(2)-C(48) 113.04(19)

290

C(41)-Fe(2)-C(48) 140.40(17) C(44)-Fe(2)-C(48) 140.11(15) C(46)-Fe(2)-C(40) 112.49(18) C(45)-Fe(2)-C(40) 110.10(19) C(49)-Fe(2)-C(40) 138.8(2) C(43)-Fe(2)-C(40) 68.59(14) C(47)-Fe(2)-C(40) 140.66(17) C(42)-Fe(2)-C(40) 68.65(15) C(41)-Fe(2)-C(40) 40.64(13) C(44)-Fe(2)-C(40) 40.58(13) C(48)-Fe(2)-C(40) 178.25(16) C(47)-C(46)-C(45) 110.5(6) C(47)-C(46)-Fe(2) 71.6(3) C(45)-C(46)-Fe(2) 70.8(3) C(46)-C(45)-C(49) 105.6(4) C(46)-C(45)-Fe(2) 69.9(3) C(49)-C(45)-Fe(2) 69.3(3) C(46)-C(47)-C(48) 109.7(6) C(46)-C(47)-Fe(2) 69.4(3) C(48)-C(47)-Fe(2) 71.3(3)

291

18. X-Ray crystallographic data for (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

Table AI-18a. Crystallographic data for Table AI-18b. Data collection

ND020409

C36H52AuP·0.5(C6H6) Bruker SMART CCD area-detector

Mr = 751.77 diffractometer

Triclinic, Pī  scans

a = 8.941(3) Å Absorption correction: multi-scan

b = 10.598(4) Å Tmin = 0.3654, Tmax = 0.7553

c = 20.008(7) Å 14048 measured reflections

α = 91.889(4) º 6557 independent reflections

 = 91.854(4) º 5897 reflections with I > 2(I)

γ = 94.823(4) º Rint = 0.0428

3 V = 1886.8(11) Å  max = 25.00º

Z = 2 h = -10  10

-3 Dx = 1.323 Mg m k = -12  12

Mo K radiation l = -23 23

Cell parameters from 8933 reflections

 = 1.02±25.00º

 = 3.964 mm-1

T = 100 (2) K

Irregular, colorless

0.32  0.21 0.08 mm

292

Table AI-18c. Refinement Figure AI-18a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent molecules are

omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0362 wR(F2) = 0.0952

S = 1.057

6557 reflections

373 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0611 P) + 0.2140 P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.186

-3 max = 1.661 eÅ

-3 min = -3.158 eÅ

Table AI-18d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.060(6) C(1)-Au(1)-P(1) 176.03(15) Au(1)-P(1) 2.3087(15) C(19)-P(1)-C(31) 105.7(2) P(1)-C(19) 1.848(5) C(19)-P(1)-C(25) 111.7(2) P(1)-C(31) 1.848(5) C(31)-P(1)-C(25) 104.4(2) P(1)-C(25) 1.853(5) C(19)-P(1)-Au(1) 113.77(18) C(7)-C(8) 1.288(10) C(31)-P(1)-Au(1) 109.35(17) C(7)-C(4) 1.480(9) C(25)-P(1)-Au(1) 111.33(18) C(4)-C(3) 1.390(9) C(8)-C(7)-C(4) 128.4(8) C(4)-C(5) 1.412(9) C(3)-C(4)-C(5) 117.3(5) C(16)-C(18) 1.521(9) C(3)-C(4)-C(7) 117.7(6) C(16)-C(17) 1.528(9) C(5)-C(4)-C(7) 125.0(6) C(16)-C(12) 1.532(8) C(18)-C(16)-C(17) 109.7(6)

293

C(16)-C(15) 1.540(9) C(18)-C(16)-C(12) 110.6(5) C(12)-C(11) 1.374(10) C(17)-C(16)-C(12) 111.9(5) C(12)-C(13) 1.407(9) C(18)-C(16)-C(15) 108.6(6) C(8)-C(9) 1.502(10) C(17)-C(16)-C(15) 107.7(5) C(9)-C(14) 1.353(11) C(12)-C(16)-C(15) 108.2(5) C(9)-C(10) 1.400(11) C(11)-C(12)-C(13) 117.2(6) C(14)-C(13) 1.379(10) C(11)-C(12)-C(16) 123.1(6) C(11)-C(10) 1.411(10) C(13)-C(12)-C(16) 119.7(6) C(1)-C(6) 1.402(8) C(7)-C(8)-C(9) 125.8(7) C(1)-C(2) 1.412(8) C(14)-C(9)-C(10) 118.0(7) C(6)-C(5) 1.391(8) C(14)-C(9)-C(8) 118.9(7) C(3)-C(2) 1.371(8) C(10)-C(9)-C(8) 123.1(7) C(20)-C(19) 1.534(7) C(9)-C(14)-C(13) 121.0(8) C(20)-C(21) 1.538(7) C(12)-C(11)-C(10) 119.9(7) C(21)-C(22) 1.523(8) C(14)-C(13)-C(12) 122.4(7) C(19)-C(24) 1.544(8) C(9)-C(10)-C(11) 121.6(7) C(23)-C(22) 1.523(8) C(6)-C(1)-C(2) 115.5(5) C(23)-C(24) 1.533(7) C(6)-C(1)-Au(1) 120.6(4) C(25)-C(26) 1.541(7) C(2)-C(1)-Au(1) 123.9(4) C(25)-C(30) 1.549(8) C(5)-C(6)-C(1) 122.3(6) C(30)-C(29) 1.538(7) C(2)-C(3)-C(4) 121.5(6) C(31)-C(32) 1.529(7) C(6)-C(5)-C(4) 120.6(6) C(31)-C(36) 1.553(6) C(3)-C(2)-C(1) 122.7(6) C(36)-C(35) 1.537(7) C(19)-C(20)-C(21) 109.8(4) C(35)-C(34) 1.524(8) C(22)-C(21)-C(20) 110.7(4) C(32)-C(33) 1.523(7) C(20)-C(19)-C(24) 110.8(4) C(33)-C(34) 1.532(7) C(20)-C(19)-P(1) 114.3(4) C(26)-C(27) 1.544(7) C(24)-C(19)-P(1) 115.0(4) C(27)-C(28) 1.522(9) C(22)-C(23)-C(24) 111.6(5) C(29)-C(28) 1.538(8) C(23)-C(24)-C(19) 109.6(4) C(38)-C(37) 1.368(11) C(21)-C(22)-C(23) 111.5(4) C(38)-C(39) 1.379(12) C(26)-C(25)-C(30) 110.1(4) C(37)-C(39)#1 1.382(10) C(26)-C(25)-P(1) 111.8(4) C(39)-C(37)#1 1.382(10) C(30)-C(25)-P(1) 117.6(4) C(29)-C(30)-C(25) 109.6(5) C(32)-C(31)-C(36) 109.5(4) C(32)-C(31)-P(1) 111.1(4) C(36)-C(31)-P(1) 110.2(4) C(35)-C(36)-C(31) 110.8(4) C(34)-C(35)-C(36) 111.6(4) C(33)-C(32)-C(31) 112.7(4) C(32)-C(33)-C(34) 111.1(4) C(35)-C(34)-C(33) 110.7(4) C(25)-C(26)-C(27) 110.6(4)

294

C(28)-C(27)-C(26) 111.3(5) C(28)-C(29)-C(30) 111.1(5) C(27)-C(28)-C(29) 111.1(5) C(37)-C(38)-C(39) 120.5(7) C(38)-C(37)-C(39)#1 120.7(8) C(38)-C(39)-C(37)#1 118.8(8)

295

19. X-Ray crystallographic data for 1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

Table AI-19a. Crystallographic data for Table AI-19b. Data collection

ND032509

C66H54Au2P2 Bruker SMART CCD area-detector

Mr = 1302.97 diffractometer

Monoclinic, P21/c  scans

a = 21.603(2) Å Absorption correction: multi-scan

b = 8.9915(9) Å Tmin = 0.3404, Tmax = 0.7148

c = 18.6285(19) Å 32622 measured reflections

α = 90.00 º 8210 independent reflections

 = 94.5350(10) º 5792 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0763

3 V = 3607.1(6) Å  max = 27.50º

Z = 2 h = -28 28

-3 Dx = 1.200 Mg m k = -11 11

Mo K radiation l = -24 23

Cell parameters from 9603 reflections

 = 0.95±27.50º

 = 4.137 mm-1

T = 100 (2) K

Irregular, yellow

0.33  0.17 0.09 mm

296

Table AI-19c. Refinement Figure AI-19a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity. The

tricyclohexyl and tert-butyl groups exhibit

disorders.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0474 wR(F2) = 0.1385

S = 1.050

8210 reflections

352 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0917 P) + 0.0000 P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.223

-3 max = 1.486 eÅ

-3 min = -2.373 eÅ

Table AI-19d. Selected geometric parameters (Å, º). Au(1)-C(1) 2.070(7) C(1)-Au(1)-P(1) 178.57(17) Au(1)-P(1) 2.3158(17) C(22A)-P(1)-C(28) 94.6(8) P(1)-C(22A) 1.747(17) C(22A)-P(1)-C(16) 114.5(6) P(1)-C(28) 1.845(9) C(28)-P(1)-C(16) 107.1(4) P(1)-C(16) 1.857(6) C(22A)-P(1)-C(22) 21.1(7) P(1)-C(22) 1.998(14) C(28)-P(1)-C(22) 115.2(7) C(5)-C(4) 1.342(9) C(16)-P(1)-C(22) 102.0(5) C(5)-C(6) 1.469(9) C(22A)-P(1)-Au(1) 115.2(6) C(6)-C(7) 1.363(11) C(28)-P(1)-Au(1) 113.5(3) C(6)-C(11) 1.388(10) C(16)-P(1)-Au(1) 110.8(2) C(3)-C(1) 1.413(9) C(22)-P(1)-Au(1) 107.7(5) C(3)-C(2)#1 1.425(9) C(4)-C(5)-C(6) 126.5(7) C(3)-C(4) 1.465(9) C(7)-C(6)-C(11) 114.2(7) C(2)-C(1) 1.411(9) C(7)-C(6)-C(5) 126.1(7) C(2)-C(3)#1 1.425(9) C(11)-C(6)-C(5) 119.5(7)

297

C(16)-C(21) 1.539(9) C(1)-C(3)-C(2)#1 118.5(6) C(16)-C(17) 1.557(9) C(1)-C(3)-C(4) 120.2(6) C(33)-C(32) 1.487(11) C(2)#1-C(3)-C(4) 121.1(6) C(33)-C(28) 1.522(11) C(1)-C(2)-C(3)#1 124.5(6) C(21)-C(20) 1.530(9) C(2)-C(1)-C(3) 116.9(6) C(17)-C(18) 1.549(10) C(2)-C(1)-Au(1) 118.9(5) C(20)-C(19) 1.555(11) C(3)-C(1)-Au(1) 124.0(5) C(18)-C(19) 1.538(11) C(5)-C(4)-C(3) 128.4(7) C(28)-C(29A) 1.29(2) C(21)-C(16)-C(17) 111.2(5) C(28)-C(29) 1.475(14) C(21)-C(16)-P(1) 110.2(4) C(9)-C(10) 1.344(14) C(17)-C(16)-P(1) 108.8(5) C(9)-C(8) 1.381(14) C(32)-C(33)-C(28) 115.8(7) C(9)-C(12) 1.554(13) C(20)-C(21)-C(16) 111.2(6) C(12)-C(15) 1.49(2) C(18)-C(17)-C(16) 110.6(6) C(12)-C(13) 1.50(2) C(21)-C(20)-C(19) 112.1(6) C(12)-C(14) 1.53(2) C(19)-C(18)-C(17) 112.2(6) C(11)-C(10) 1.419(11) C(29A)-C(28)-C(29) 29.8(8) C(8)-C(7) 1.363(12) C(29A)-C(28)-C(33) 123.9(12) C(30)-C(29) 1.469(14) C(29)-C(28)-C(33) 120.0(8) C(30)-C(31A) 1.59(2) C(29A)-C(28)-P(1) 116.7(11) C(30)-C(31B) 1.60(3) C(29)-C(28)-P(1) 118.4(7) C(30)-C(29A) 1.65(2) C(33)-C(28)-P(1) 118.1(6) C(32)-C(31A) 1.36(2) C(10)-C(9)-C(8) 115.2(8) C(32)-C(31B) 1.59(2) C(10)-C(9)-C(12) 122.1(9) C(29)-C(29A) 0.732(18) C(8)-C(9)-C(12) 122.7(10) C(23)-C(24) 1.48(2) C(15)-C(12)-C(13) 117.7(18) C(23)-C(22) 1.542(18) C(15)-C(12)-C(14) 113.8(16) C(23)-C(22A) 1.618(19) C(13)-C(12)-C(14) 99.1(12) C(23)-C(24A) 1.72(3) C(15)-C(12)-C(9) 105.0(10) C(22)-C(22A) 0.728(18) C(13)-C(12)-C(9) 109.8(10) C(22)-C(27) 1.303(19) C(14)-C(12)-C(9) 111.6(10) C(26)-C(27) 1.541(12) C(6)-C(11)-C(10) 121.7(8) C(26)-C(25) 1.554(15) C(9)-C(10)-C(11) 122.2(9) C(25)-C(24) 1.34(3) C(7)-C(8)-C(9) 122.9(10) C(25)-C(24A) 1.41(4) C(8)-C(7)-C(6) 123.5(8) C(24)-C(24A) 0.75(4) C(29)-C(30)-C(31A) 113.7(9) C(31A)-C(31B) 0.92(3) C(29)-C(30)-C(31B) 114.8(12) C(22A)-C(27) 1.458(19) C(31A)-C(30)-C(31B) 33.4(10) C(29)-C(30)-C(29A) 26.4(8) C(31A)-C(30)-C(29A) 103.2(10) C(31B)-C(30)-C(29A) 120.0(12) C(31A)-C(32)-C(33) 116.3(10) C(31A)-C(32)-C(31B) 35.1(12) C(33)-C(32)-C(31B) 123.4(11)

298

C(29A)-C(29)-C(30) 90(2) C(29A)-C(29)-C(28) 61(2) C(30)-C(29)-C(28) 117.0(11) C(24)-C(23)-C(22) 110.2(11) C(24)-C(23)-C(22A) 113.4(12) C(22)-C(23)-C(22A) 26.5(7) C(24)-C(23)-C(24A) 25.8(16) C(22)-C(23)-C(24A) 107.7(16) C(22A)-C(23)-C(24A) 122.8(15) C(22A)-C(22)-C(27) 87(2) C(22A)-C(22)-C(23) 83(2) C(27)-C(22)-C(23) 125.1(13) C(22A)-C(22)-P(1) 60(2) C(27)-C(22)-P(1) 111.1(10) C(23)-C(22)-P(1) 109.0(9) C(18)-C(19)-C(20) 108.5(7) C(27)-C(26)-C(25) 114.1(8) C(24)-C(25)-C(24A) 31.5(15) C(24)-C(25)-C(26) 119.5(11) C(24A)-C(25)-C(26) 124.4(19) C(24A)-C(24)-C(25) 80(4) C(24A)-C(24)-C(23) 95(4) C(25)-C(24)-C(23) 125.3(16) C(31B)-C(31A)-C(32) 86(2) C(31B)-C(31A)-C(30) 74(2) C(32)-C(31A)-C(30) 120.6(14) C(31A)-C(31B)-C(32) 58.8(18) C(31A)-C(31B)-C(30) 72(2) C(32)-C(31B)-C(30) 107.0(13) C(29)-C(29A)-C(28) 89(2) C(29)-C(29A)-C(30) 63(2) C(28)-C(29A)-C(30) 117.0(14) C(22)-C(22A)-C(27) 63(2) C(22)-C(22A)-C(23) 71(2) C(27)-C(22A)-C(23) 110.4(12) C(22)-C(22A)-P(1) 99(2) C(27)-C(22A)-P(1) 118.0(13) C(23)-C(22A)-P(1) 118.6(10) C(24)-C(24A)-C(25) 69(4) C(24)-C(24A)-C(23) 59(3) C(25)-C(24A)-C(23) 105.7(17) C(22)-C(27)-C(22A) 29.9(8) C(22)-C(27)-C(26) 117.0(10) C(22A)-C(27)-C(26) 124.6(11)

299

20. X-Ray crystallographic data for

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

Table AI-20a. Crystallographic data for Table AI-20b. Data collection

TetraGold_09mz353_0m

C102H146Au4P4· 3.63(CHCl3) Bruker SMART CCD area-detector

Mr = 2717.03 diffractometer

Monoclinic, P21/n  scans

a = 17.794(3) Å Absorption correction: multi-scan

b = 17.242(3) Å Tmin = 0.3075, Tmax = 0.7464

c = 20.266(3) Å 37494 measured reflections

α = 90.00 º 12049 independent reflections

 = 108.272(2) º 8510 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0474

3 V = 5904.0(15) Å  max = 26.37º

Z = 2 h = -22 20

-3 Dx = 1.528 Mg m k = -21 16

Mo K radiation l = -25 25

Cell parameters from 3774 reflections

 = 1.33±26.37º

 = 5.295 mm-1

T = 100 (2) K

Plate, orange

0.45  0.40 0.20 mm

300

Table AI-20c. Refinement Figure AI-20a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent are omitted for

clarity. The tricyclohexyl and exhibit disorders.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0692 wR(F2) = 0.2040

S = 1.109

12049 reflections

612 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.1440 P) + 0.0000 P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.223

-3 max = 1.486 eÅ

-3 min = -2.373 eÅ

Table AI-20d. Selected geometric parameters (Å, º). C1-C2 1.502(16) C2-C1-C6 111.9(10) C1-C6 1.509(17) C2-C1-P1 116.4(9) C1-P1 1.824(13) C6-C1-P1 111.9(8) C2-C3 1.516(19) C1-C2-C3 109.4(11) C3-C4 1.55(2) C2-C3-C4 110.5(12) C4-C5 1.43(2) C5-C4-C3 108.9(14) C5-C6 1.530(19) C4-C5-C6 113.2(12) C7-C12 1.510(17) C1-C6-C5 110.4(10) C7-C8 1.514(17) C12-C7-C8 110.9(10) C7-P1 1.826(12) C12-C7-P1 113.7(9) C8-C9 1.492(17) C8-C7-P1 115.4(9) C9-C10 1.470(19) C9-C8-C7 112.4(11) C10-C11 1.56(2) C10-C9-C8 112.5(12) C11-C12 1.349(19) C9-C10-C11 109.3(12) C13-C14 1.51(2) C12-C11-C10 115.7(13) C13-C18 1.532(18) C11-C12-C7 113.9(12) 301

C13-P1 1.839(12) C14-C13-C18 112.1(12) C14-C15 1.55(2) C14-C13-P1 110.0(9) C15-C16 1.49(3) C18-C13-P1 109.1(9) C16-C17 1.51(3) C13-C14-C15 107.4(13) C17-C18 1.51(2) C16-C15-C14 113.2(15) C19-C20 1.172(15) C15-C16-C17 106.8(16) C19-Au1 1.983(13) C16-C17-C18 109.2(14) C20-C21 1.425(13) C17-C18-C13 112.0(13) C21-C26 1.385(14) C20-C19-Au1 174.6(10) C21-C22 1.396(16) C19-C20-C21 178.7(13) C22-C23 1.374(14) C26-C21-C22 117.2(9) C23-C24 1.385(13) C26-C21-C20 123.6(10) C24-C25 1.381(15) C22-C21-C20 119.1(9) C24-C27 1.461(13) C23-C22-C21 120.9(10) C25-C26 1.361(14) C22-C23-C24 120.3(10) C27-C28 1.313(14) C25-C24-C23 119.0(9) C28-C29 1.414(13) C25-C24-C27 118.7(9) C29-C30 1.391(12) C23-C24-C27 122.3(9) C29-C31 1.392(13) C26-C25-C24 120.2(9) C30-C31 1.385(12) C25-C26-C21 122.2(10) C30-C29 1.391(12) C28-C27-C24 125.7(9) C31-C32 1.419(12) C27-C28-C29 128.8(9) C32-C33 1.179(13) C30-C29-C31 118.0(8) C33-Au2 2.001(10) C30-C29-C28 122.2(9) C34-C35 1.529(15) C31-C29-C28 119.7(8) C34-C39 1.544(19) C31-C30-C29 122.2(8) C34-P2 1.808(12) C30-C31-C29 119.8(8) C35-C36 1.473(17) C30-C31-C32 119.8(8) C36-C37 1.44(2) C29-C31-C32 120.4(8) C37-C38 1.54(2) C33-C32-C31 175.6(10) C38-C39 1.50(2) C32-C33-Au2 176.2(9) C40-C41 1.498(16) C35-C34-C39 111.0(11) C40-C45 1.507(17) C35-C34-P2 119.2(8) C40-P2 1.845(15) C39-C34-P2 110.6(9) C41-C42 1.537(17) C36-C35-C34 112.3(10) C42-C43 1.534(19) C37-C36-C35 112.7(14) C43-C44 1.53(2) C36-C37-C38 113.4(12) C44-C45 1.557(19) C39-C38-C37 112.3(13) Au1-P1 2.261(3) C38-C39-C34 109.5(13) Au2-P2 2.263(3) C41-C40-C45 109(2) C40B-C41B 1.511(15) C41-C40-P2 109.6(13) C40B-C45B 1.520(15) C45-C40-P2 113.4(15) C40B-P2 1.862(17) C40-C41-C42 115(2) C41B-C42B 1.550(19) C43-C42-C41 111(3)

302

C42B-C43B 1.54(2) C42-C43-C44 110(3) C43B-C44B 1.54(2) C43-C44-C45 108(2) C44B-C45B 1.56(2) C40-C45-C44 102(3) C46-C51 1.480(18) C19-Au1-P1 175.5(3) C46-C47 1.497(16) C33-Au2-P2 177.6(3) C46-P2 1.823(13) C41B-C40B-C45B 125.4(19) C47-C48 1.53(2) C41B-C40B-P2 123.6(18) C48-C49 1.41(2) C45B-C40B-P2 107.4(14) C49-C50 1.50(2) C40B-C41B-C42B 105(2) C50-C51 1.49(2) C43B-C42B-C41B 124(3) C52-Cl2 1.704(18) C42B-C43B-C44B 101(4) C52-Cl3 1.707(14) C43B-C44B-C45B 117(3) C52-Cl1 1.735(17) C40B-C45B-C44B 116(3) C53-Cl4 1.53(3) C51-C46-C47 110.4(11) C53-Cl6 1.66(3) C51-C46-P2 111.6(8) C53-Cl5 1.76(4) C47-C46-P2 110.1(9) C46-C47-C48 113.0(12) C49-C48-C47 111.0(12) C48-C49-C50 112.1(16) C51-C50-C49 110.2(12) C46-C51-C50 112.0(15) Cl2-C52-Cl3 112.1(10) Cl2-C52-Cl1 112.6(8) Cl3-C52-Cl1 110.6(9) C1-P1-C7 107.6(6) C1-P1-C13 106.9(6) C7-P1-C13 109.6(6) C1-P1-Au1 110.5(4) C7-P1-Au1 113.8(4) C13-P1-Au1 108.1(4) C34-P2-C46 106.6(5) C34-P2-C40 117.6(9) C46-P2-C40 104.5(8) C34-P2 C40B 102.7(9) C46-P2-C40B 110.0(9) C34-P2-Au2 108.9(3) C46-P2-Au2 111.1(4) C40-P2-Au2 108.2(7) C40B-P2-Au2 116.8(7) Cl4-C53-Cl6 122(2) Cl4-C53-Cl5 105.8(18) Cl6-C53-Cl5 108(2)

303

21. X-Ray crystallographic data for (PPhMe2Au)LaBr2

Table AI-21a. Crystallographic data for Table AI-21b. Data collection

ND101909_mz

C40H29AuBr4N3P Bruker SMART CCD

Mr = 1099.24 area-detector diffractometer

Monoclinic, P21/c  scans

a = 15.1906(10) Å Absorption correction: multi-scan

b = 22.9712(15) Å Tmin = 0.3046, Tmax = 0.7458

c = 10.4280(7) Å 33302 measured reflections

α = 90.00 º 8783 independent reflections

 = 91.6570(10) º 6920 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0428

3 V = 3637.3(4) Å  max = 28.28º

Z = 4 h = -20  19

-3 Dx = 2.007 Mg m k = -29  27

Mo K radiation l = -13 12

Cell parameters from 3664 reflections

 = 1.34±28.28º

 = 8.517 mm-1

T = 100 (2) K

chunk, black

0.44  0.27 0.06 mm

304

Table AI-21c. Refinement Figure AI-21a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0364 wR(F2) = 0.0841

S = 1.024

8783 reflections

444 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0423P) + 4.4562P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.148

-3 max = 1.864 eÅ

-3 min = -1.863 eÅ

Table AI-21d. Selected geometric parameters (Å, º). Au1-N1 2.140(3) N1-Au1-P1 155.05(9) Au1-P1 2.2093(12) N1-Au1-N2 77.29(12) Au1-N2 2.420(4) P1-Au1-N2 125.29(9) Br1-C12 1.899(5) N1-C1-C2 110.8(4) Br2-C18 1.914(5) N1-C1-C9 121.8(4) Br3-C24 1.897(5) C2-C1-C9 127.3(4) Br4-C30 1.898(4) C3-C2-C1 108.0(4) C1-N1 1.343(5) C2-C3-C4 105.7(4) C1-C2 1.418(6) C2-C3-C15 126.6(4) C1-C9 1.455(6) C4-C3-C15 127.6(4) C2-C3 1.366(6) N3-C4-N1 128.0(4) C3-C4 1.454(5) N3-C4-C3 123.2(4) C3-C15 1.471(6) N1-C4-C3 108.7(3) C4-N3 1.324(5) N3-C5-N2 126.6(4) C4-N1 1.400(5) N3-C5-C6 123.5(4) C5-N3 1.328(5) N2-C5-C6 109.9(4) C5-N2 1.383(5) C7-C6-C5 105.1(4)

305

C5-C6 1.461(6) C7-C6-C21 126.6(4) C6-C7 1.372(6) C5-C6-C21 128.2(4) C6-C21 1.462(6) C6-C7-C8 107.3(4) C7-C8 1.421(6) N2-C8-C7 111.8(4) C8-N2 1.340(5) N2-C8-C27 121.8(4) C8-C27 1.461(6) C7-C8-C27 126.4(4) C9-C10 1.390(6) C10-C9-C14 118.4(4) C9-C14 1.394(6) C10-C9-C1 121.1(4) C10-C11 1.380(8) C14-C9-C1 120.4(4) C11-C12 1.381(8) C11-C10-C9 120.8(5) C12-C13 1.371(8) C10-C11-C12 119.2(5) C13-C14 1.381(7) C13-C12-C11 121.5(5) C15-C20 1.393(6) C13-C12-Br1 119.3(5) C15-C16 1.394(6) C11-C12-Br1 119.2(4) C16-C17 1.383(6) C12-C13-C14 118.8(5) C17-C18 1.353(8) C13-C14-C9 121.2(4) C18-C19 1.383(8) C20-C15-C16 118.0(4) C19-C20 1.384(6) C20-C15-C3 123.1(4) C21-C22 1.396(6) C16-C15-C3 118.7(4) C21-C26 1.398(6) C17-C16-C15 121.3(5) C22-C23 1.386(7) C18-C17-C16 118.9(5) C23-C24 1.369(7) C17-C18-C19 122.2(5) C24-C25 1.379(8) C17-C18-Br2 119.2(4) C25-C26 1.378(7) C19-C18-Br2 118.6(4) C27-C28 1.398(7) C18-C19-C20 118.6(5) C27-C32 1.400(6) C19-C20-C15 120.9(5) C28-C29 1.383(6) C22-C21-C26 117.1(4) C29-C30 1.382(6) C22-C21-C6 123.4(4) C30-C31 1.384(7) C26-C21-C6 119.5(4) C31-C32 1.375(6) C23-C22-C21 121.1(4) C33-P1 1.815(5) C24-C23-C22 119.9(5) C34-P1 1.815(5) C23-C24-C25 120.8(5) C35-C36 1.371(7) C23-C24-Br3 120.1(4) C35-C40 1.387(7) C25-C24-Br3 119.0(4) C35-P1 1.816(5) C26-C25-C24 118.9(5) C36-C37 1.415(8) C25-C26-C21 122.2(5) C37-C38 1.356(8) C28-C27-C32 118.1(4) C38-C39 1.358(8) C28-C27-C8 121.3(4) C39-C40 1.390(8) C32-C27-C8 120.6(4) C29-C28-C27 121.3(4) C30-C29-C28 118.6(4) C29-C30-C31 122.0(4) C29-C30-Br4 119.0(4) C31-C30-Br4 119.0(3)

306

C32-C31-C30 118.6(4) C31-C32-C27 121.5(5) C36-C35-C40 118.6(5) C36-C35-P1 120.2(4) C40-C35-P1 121.0(4) C35-C36-C37 120.2(5) C38-C37-C36 119.8(5) C37-C38-C39 120.5(5) C38-C39-C40 120.3(5) C35-C40-C39 120.5(5) C1-N1-Au1 122.0(3) C4-N1-Au1 122.8(3) C8-N2-C5 106.0(4) C8-N2-Au1 128.9(3) C5-N2-Au1 119.0(2) C4-N3-C5 125.8(4) C34-P1-C33 102.9(3) C34-P1-C35 102.0(2) C33-P1-C35 105.4(2) C34-P1-Au1 117.05(17) C33-P1-Au1 109.75(18) C35-P1-Au1 118.18(15)

307

22. X-Ray crystallographic data for (PPhMe2Au)LaBr2

Table AI-22a. Crystallographic data for Table AI-22b. Data collection

ND120209

C40H31AuBr2N3P Bruker SMART CCD area-detector

Mr = 941.43 diffractometer

Monoclinic, P21/c  scans

a = 12.4081(10) Å Absorption correction: multi-scan

b = 14.4032(12) Å Tmin = 0.3065, Tmax = 0.4078

c = 22.5506(19) Å 44498 measured reflections

α = 90.00 º 8731 independent reflections

 = 102.7230(10) º 7155 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0372

3 V = 3931.2(6) Å  max = 27.33º

Z = 4 h = -15  15

-3 Dx = 1.832 Mg m k = -18  18

Mo K radiation l = -28 28

Cell parameters from 9945 reflections

 = 1.68±27.33º

 = 5.845 mm-1

T = 170(2) K

irregular, red

0.27  0.13 0.19 mm

308

Table AI-22c. Refinement Figure AI-22a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0263 wR(F2) = 0.0601

S = 1.084

8731 reflections

426 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0307P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.101

-3 max = 0.769 eÅ

-3 min = -0.952 eÅ

Table AI-22d. Selected geometric parameters (Å, º). Au(1)-N(3) 2.119(2) N(3)-Au(1)-P(1) 158.48(7) Au(1)-P(1) 2.2071(8) N(3)-Au(1)-N(1) 79.78(8) Au(1)-N(1) 2.490(2) P(1)-Au(1)-N(1) 121.57(6) Br(2)-C(3) 1.875(3) C(31)-C(30)-C(29) 119.4(3) Br(3)-C(19) 1.896(3) C(6)-C(5)-C(10) 119.6(3) C(30)-C(31) 1.357(5) C(6)-C(5)-C(4) 118.9(3) C(30)-C(29) 1.381(5) C(10)-C(5)-C(4) 121.4(3) C(5)-C(6) 1.385(4) C(19)-C(18)-C(17) 104.4(3) C(5)-C(10) 1.400(4) C(19)-C(18)-C(27) 129.3(3) C(5)-C(4) 1.470(4) C(17)-C(18)-C(27) 126.2(3) C(18)-C(19) 1.362(4) C(8)-C(7)-C(6) 119.8(3) C(18)-C(17) 1.427(4) C(11)-C(12)-C(13) 120.8(3) C(18)-C(27) 1.473(4) N(2)-C(17)-N(3) 128.5(2) C(7)-C(8) 1.390(5) N(2)-C(17)-C(18) 121.6(2) C(7)-C(6) 1.394(4) N(3)-C(17)-C(18) 109.9(2) C(12)-C(11) 1.383(4) C(34)-C(33)-C(38) 118.2(3) C(12)-C(13) 1.386(4) C(34)-C(33)-P(1) 120.9(2)

309

C(17)-N(2) 1.336(3) C(38)-C(33)-P(1) 121.0(3) C(17)-N(3) 1.386(3) C(3)-C(2)-C(1) 104.3(2) C(33)-C(34) 1.370(4) C(3)-C(2)-C(11) 130.4(3) C(33)-C(38) 1.388(4) C(1)-C(2)-C(11) 125.3(2) C(33)-P(1) 1.810(3) C(9)-C(10)-C(5) 119.5(3) C(2)-C(3) 1.361(4) N(3)-C(20)-C(19) 108.9(3) C(2)-C(1) 1.454(4) N(3)-C(20)-C(21) 121.5(3) C(2)-C(11) 1.464(4) C(19)-C(20)-C(21) 129.6(3) C(10)-C(9) 1.374(4) C(23)-C(22)-C(21) 120.5(3) C(20)-N(3) 1.352(3) N(2)-C(1)-N(1) 127.8(3) C(20)-C(19) 1.399(4) N(2)-C(1)-C(2) 121.7(2) C(20)-C(21) 1.472(4) N(1)-C(1)-C(2) 110.5(2) C(22)-C(23) 1.377(5) N(1)-C(4)-C(3) 110.7(2) C(22)-C(21) 1.396(4) N(1)-C(4)-C(5) 121.3(3) C(1)-N(2) 1.317(3) C(3)-C(4)-C(5) 128.0(3) C(1)-N(1) 1.388(3) C(26)-C(21)-C(22) 118.0(3) C(4)-N(1) 1.328(3) C(26)-C(21)-C(20) 121.2(3) C(4)-C(3) 1.438(4) C(22)-C(21)-C(20) 120.7(3) C(21)-C(26) 1.387(4) C(24)-C(23)-C(22) 120.6(3) C(23)-C(24) 1.370(5) C(12)-C(11)-C(16) 118.1(3) C(11)-C(16) 1.404(4) C(12)-C(11)-C(2) 121.4(3) C(13)-C(14) 1.375(4) C(16)-C(11)-C(2) 120.4(3) C(28)-C(29) 1.372(4) C(14)-C(13)-C(12) 120.5(3) C(28)-C(27) 1.393(4) C(2)-C(3)-C(4) 108.3(2) C(32)-C(27) 1.381(4) C(2)-C(3)-Br(2) 126.2(2) C(32)-C(31) 1.384(4) C(4)-C(3)-Br(2) 125.5(2) C(38)-C(37) 1.375(5) C(18)-C(19)-C(20) 110.0(3) C(14)-C(15) 1.378(5) C(18)-C(19)-Br(3) 125.3(2) C(26)-C(25) 1.373(5) C(20)-C(19)-Br(3) 124.6(2) C(24)-C(25) 1.377(5) C(29)-C(28)-C(27) 120.1(3) C(16)-C(15) 1.372(4) C(27)-C(32)-C(31) 120.1(3) C(36)-C(37) 1.359(5) C(37)-C(38)-C(33) 120.6(3) C(36)-C(35) 1.366(5) C(13)-C(14)-C(15) 119.2(3) C(34)-C(35) 1.389(5) C(25)-C(26)-C(21) 120.8(3) C(8)-C(9) 1.380(5) C(32)-C(27)-C(28) 118.8(3) P(1)-C(40) 1.796(4) C(32)-C(27)-C(18) 120.4(3) P(1)-C(39) 1.806(3) C(28)-C(27)-C(18) 120.7(3) C(23)-C(24)-C(25) 119.4(3) C(5)-C(6)-C(7) 120.2(3) C(28)-C(29)-C(30) 120.7(3) C(15)-C(16)-C(11) 120.3(3) C(16)-C(15)-C(14) 121.0(3) C(37)-C(36)-C(35) 119.6(3) C(36)-C(37)-C(38) 120.7(3)

310

C(26)-C(25)-C(24) 120.5(3) C(33)-C(34)-C(35) 120.8(3) C(9)-C(8)-C(7) 119.6(3) C(30)-C(31)-C(32) 120.9(3) C(10)-C(9)-C(8) 121.3(3) C(36)-C(35)-C(34) 120.2(4) C(1)-N(2)-C(17) 127.9(2) C(4)-N(1)-C(1) 106.2(2) C(4)-N(1)-Au(1) 129.56(18) C(1)-N(1)-Au(1) 116.38(17) C(20)-N(3)-C(17) 106.8(2) C(20)-N(3)-Au(1) 122.27(19) C(17)-N(3)-Au(1) 126.79(19) C(40)-P(1)-C(39) 104.84(18) C(40)-P(1)-C(33) 105.03(16) C(39)-P(1)-C(33) 103.70(15) C(40)-P(1)-Au(1) 115.03(13) C(39)-P(1)-Au(1) 112.71(12) C(33)-P(1)-Au(1) 114.38(11)

311

23. X-Ray crystallographic data for (PPhMe2Au)LbBr2

Table AI-23a. Crystallographic data for Table AI-23b. Data collection

ND021210

C42H35AuBr2N3O2P Bruker SMART CCD area-detector

Mr = 1001.49 diffractometer

Monoclinic, Cc  scans

a = 19.8704(13) Å Absorption correction: multi-scan

b = 16.1637(11) Å Tmin = 0.4284, Tmax = 0.7461

c = 23.2378(16) Å 44588 measured reflections

α = 90.00 º 17379 independent reflections

 = 97.7000(10) º 15000 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0397

3 V = 7396.2(9) Å  max = 28.00º

Z = 8 h = -25  25

-3 Dx = 1.799 Mg m k = -21  21

Mo K radiation l = -30 30

Cell parameters from 9970 reflections

 = 1.77±28.00º

 = 6.224 mm-1

T = 170(2) K

irregular, gold

0.16  0.16 0.05 mm

312

Table AI-23c. Refinement Figure AI-23a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0312 wR(F2) = 0.0553

S = 0.923

17379 reflections

927 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0000P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.103

-3 max = 0.989 eÅ

-3 min = -0.902 eÅ

Table AI-23d. Selected geometric parameters (Å, º). Au(1)-N(3) 2.111(4) N(3)-Au(1)-P(1) 167.95(11) Au(1)-P(1) 2.2282(13) N(3)-Au(1)-N(1) 76.90(14) Au(1)-N(1) 2.602(4) P(1)-Au(1)-N(1) 114.51(10) Au(2)-N(6) 2.104(4) N(6)-Au(2)-P(2) 166.29(12) Au(2)-P(2) 2.2287(13) N(6)-Au(2)-N(4) 78.46(15) Au(2)-N(4) 2.581(4) P(2)-Au(2)-N(4) 114.56(10) Br(2)-C(20) 1.890(5) C(84)-P(2)-C(83) 101.6(3) Br(1)-C(3) 1.872(5) C(84)-P(2)-C(77) 105.4(3) Br(3)-C(45) 1.883(5) C(83)-P(2)-C(77) 104.5(3) Br(4)-C(62) 1.882(5) C(84)-P(2)-Au(2) 115.8(2) P(2)-C(84) 1.807(6) C(83)-P(2)-Au(2) 114.3(2) P(2)-C(83) 1.808(6) C(77)-P(2)-Au(2) 113.88(18) P(2)-C(77) 1.810(5) C(42)-P(1)-C(41) 100.9(3) P(1)-C(42) 1.804(5) C(42)-P(1)-C(35) 104.7(2) P(1)-C(41) 1.808(5) C(41)-P(1)-C(35) 105.7(3) P(1)-C(35) 1.815(6) C(42)-P(1)-Au(1) 116.06(19) C(23)-C(22) 1.389(7) C(41)-P(1)-Au(1) 114.18(19)

313

C(23)-C(24) 1.390(7) C(35)-P(1)-Au(1) 113.93(18) C(5)-C(6) 1.390(7) C(22)-C(23)-C(24) 120.7(5) C(5)-C(10) 1.405(7) C(6)-C(5)-C(10) 117.8(5) C(5)-C(4) 1.451(8) C(6)-C(5)-C(4) 118.6(5) C(21)-N(3) 1.351(6) C(10)-C(5)-C(4) 123.5(5) C(21)-C(20) 1.399(7) N(3)-C(21)-C(20) 109.3(4) C(21)-C(22) 1.476(7) N(3)-C(21)-C(22) 123.2(4) C(12)-C(17) 1.397(8) C(20)-C(21)-C(22) 127.5(5) C(12)-C(13) 1.400(7) C(17)-C(12)-C(13) 117.3(5) C(12)-C(2) 1.470(8) C(17)-C(12)-C(2) 121.7(5) C(20)-C(19) 1.386(7) C(13)-C(12)-C(2) 121.0(5) C(18)-N(2) 1.334(7) C(19)-C(20)-C(21) 109.8(5) C(18)-N(3) 1.384(6) C(19)-C(20)-Br(2) 125.7(4) C(18)-C(19) 1.431(7) C(21)-C(20)-Br(2) 124.2(4) C(3)-C(2) 1.375(7) N(2)-C(18)-N(3) 128.2(5) C(3)-C(4) 1.446(7) N(2)-C(18)-C(19) 120.8(4) C(25)-O(2) 1.363(6) N(3)-C(18)-C(19) 110.7(4) C(25)-C(24) 1.393(8) C(2)-C(3)-C(4) 108.5(5) C(25)-C(26) 1.406(7) C(2)-C(3)-Br(1) 124.9(4) C(4)-N(1) 1.349(7) C(4)-C(3)-Br(1) 126.3(4) C(22)-C(27) 1.408(7) O(2)-C(25)-C(24) 125.4(5) C(1)-N(2) 1.336(6) O(2)-C(25)-C(26) 115.0(5) C(1)-N(1) 1.364(7) C(24)-C(25)-C(26) 119.4(5) C(1)-C(2) 1.441(7) N(1)-C(4)-C(3) 109.1(5) C(26)-C(27) 1.369(7) N(1)-C(4)-C(5) 120.2(5) C(14)-C(13) 1.381(8) C(3)-C(4)-C(5) 130.8(5) C(14)-C(15) 1.390(9) C(23)-C(22)-C(27) 118.7(5) C(17)-C(16) 1.386(8) C(23)-C(22)-C(21) 122.1(5) C(15)-C(16) 1.369(9) C(27)-C(22)-C(21) 119.2(5) C(35)-C(40) 1.365(8) N(2)-C(1)-N(1) 126.2(5) C(35)-C(36) 1.386(7) N(2)-C(1)-C(2) 121.9(5) C(40)-C(39) 1.388(8) N(1)-C(1)-C(2) 111.9(5) C(36)-C(37) 1.384(7) C(23)-C(24)-C(25) 120.1(5) C(38)-C(37) 1.356(8) C(3)-C(2)-C(1) 103.7(5) C(38)-C(39) 1.374(9) C(3)-C(2)-C(12) 129.9(5) C(29)-C(34) 1.389(7) C(1)-C(2)-C(12) 126.3(5) C(29)-C(30) 1.397(7) C(27)-C(26)-C(25) 120.0(5) C(29)-C(19) 1.467(7) C(13)-C(14)-C(15) 119.9(6) C(32)-C(33) 1.375(8) C(16)-C(17)-C(12) 120.8(6) C(32)-C(31) 1.384(7) C(26)-C(27)-C(22) 121.0(5) C(6)-C(7) 1.396(8) C(16)-C(15)-C(14) 119.2(6) C(33)-C(34) 1.399(8) C(15)-C(16)-C(17) 121.1(6) C(30)-C(31) 1.384(7) C(40)-C(35)-C(36) 118.3(5) N(6)-C(63) 1.347(6) C(40)-C(35)-P(1) 121.1(4)

314

N(6)-C(60) 1.395(6) C(36)-C(35)-P(1) 120.6(4) N(5)-C(43) 1.310(6) C(35)-C(40)-C(39) 121.3(6) N(5)-C(60) 1.350(7) C(37)-C(36)-C(35) 121.0(5) N(4)-C(46) 1.333(7) C(37)-C(38)-C(39) 121.0(6) N(4)-C(43) 1.397(6) C(38)-C(37)-C(36) 119.4(6) C(77)-C(78) 1.391(7) C(34)-C(29)-C(30) 118.1(5) C(77)-C(82) 1.391(7) C(34)-C(29)-C(19) 121.0(5) C(82)-C(81) 1.378(8) C(30)-C(29)-C(19) 120.8(4) C(78)-C(79) 1.376(7) C(33)-C(32)-C(31) 120.3(5) C(81)-C(80) 1.383(9) C(5)-C(6)-C(7) 122.6(5) C(80)-C(79) 1.390(9) C(32)-C(33)-C(34) 120.5(6) C(48)-C(49) 1.383(8) C(31)-C(30)-C(29) 121.7(5) C(48)-C(47) 1.415(7) C(20)-C(19)-C(18) 103.4(4) C(69)-C(68) 1.381(8) C(20)-C(19)-C(29) 130.6(5) C(69)-C(64) 1.404(7) C(18)-C(19)-C(29) 126.0(4) C(64)-C(65) 1.395(7) C(29)-C(34)-C(33) 120.2(5) C(64)-C(63) 1.463(7) C(63)-N(6)-C(60) 107.3(4) C(62)-C(61) 1.366(7) C(63)-N(6)-Au(2) 124.0(4) C(62)-C(63) 1.418(7) C(60)-N(6)-Au(2) 123.1(3) C(43)-C(44) 1.446(7) C(43)-N(5)-C(60) 127.3(5) C(47)-C(52) 1.393(7) C(46)-N(4)-C(43) 105.8(4) C(47)-C(46) 1.461(7) C(46)-N(4)-Au(2) 133.2(4) O(4)-C(67) 1.369(6) C(43)-N(4)-Au(2) 115.5(3) O(4)-C(70) 1.418(7) C(78)-C(77)-C(82) 118.6(5) C(49)-C(50) 1.371(8) C(78)-C(77)-P(2) 120.9(4) C(45)-C(44) 1.358(7) C(82)-C(77)-P(2) 120.5(4) C(45)-C(46) 1.451(7) C(81)-C(82)-C(77) 120.7(6) O(3)-C(50) 1.358(7) C(82)-C(81)-C(80) 120.6(6) O(3)-C(53) 1.436(7) C(81)-C(80)-C(79) 118.9(6) C(44)-C(54) 1.475(7) C(49)-C(48)-C(47) 120.5(5) C(50)-C(51) 1.395(8) C(68)-C(69)-C(64) 122.7(5) C(67)-C(66) 1.378(7) C(65)-C(64)-C(69) 116.2(5) C(67)-C(68) 1.384(8) C(65)-C(64)-C(63) 121.4(5) C(60)-C(61) 1.430(7) C(69)-C(64)-C(63) 122.4(5) C(52)-C(51) 1.374(7) C(61)-C(62)-C(63) 108.7(5) C(61)-C(71) 1.486(7) C(61)-C(62)-Br(4) 125.2(4) C(65)-C(66) 1.376(7) C(63)-C(62)-Br(4) 125.5(4) C(71)-C(72) 1.384(8) N(5)-C(43)-N(4) 127.2(5) C(71)-C(76) 1.402(7) N(5)-C(43)-C(44) 121.8(5) C(10)-C(9) 1.373(7) N(4)-C(43)-C(44) 111.0(4) C(8)-O(1) 1.362(7) C(52)-C(47)-C(48) 117.1(5) C(8)-C(7) 1.390(8) C(52)-C(47)-C(46) 119.1(5) C(8)-C(9) 1.394(8) C(48)-C(47)-C(46) 123.8(5) O(2)-C(28) 1.426(7) C(67)-O(4)-C(70) 118.1(5)

315

C(59)-C(58) 1.388(7) C(50)-C(49)-C(48) 120.9(5) C(59)-C(54) 1.413(7) C(44)-C(45)-C(46) 108.5(5) C(54)-C(55) 1.400(7) C(44)-C(45)-Br(3) 126.1(4) C(73)-C(72) 1.379(8) C(46)-C(45)-Br(3) 125.5(4) C(73)-C(74) 1.383(8) N(4)-C(46)-C(45) 110.3(5) C(76)-C(75) 1.372(8) N(4)-C(46)-C(47) 120.1(5) C(74)-C(75) 1.378(9) C(45)-C(46)-C(47) 129.6(5) O(1)-C(11) 1.418(7) C(50)-O(3)-C(53) 117.0(5) C(58)-C(57) 1.353(8) C(45)-C(44)-C(43) 104.4(5) C(57)-C(56) 1.372(8) C(45)-C(44)-C(54) 129.2(5) C(55)-C(56) 1.387(9) C(43)-C(44)-C(54) 126.1(5) N(6)-C(63)-C(62) 109.2(5) N(6)-C(63)-C(64) 122.2(5) C(62)-C(63)-C(64) 128.4(5) O(3)-C(50)-C(49) 115.4(5) O(3)-C(50)-C(51) 124.8(6) C(49)-C(50)-C(51) 119.8(5) O(4)-C(67)-C(66) 116.2(5) O(4)-C(67)-C(68) 124.3(5) C(66)-C(67)-C(68) 119.5(5) C(69)-C(68)-C(67) 119.1(5) N(5)-C(60)-N(6) 130.4(5) N(5)-C(60)-C(61) 120.2(5) N(6)-C(60)-C(61) 109.0(5) C(51)-C(52)-C(47) 122.4(5) C(62)-C(61)-C(60) 105.7(5) C(62)-C(61)-C(71) 129.8(5) C(60)-C(61)-C(71) 124.5(5) C(66)-C(65)-C(64) 121.5(5) C(65)-C(66)-C(67) 120.9(5) C(52)-C(51)-C(50) 119.4(5) C(21)-N(3)-C(18) 106.7(4) C(21)-N(3)-Au(1) 123.4(3) C(18)-N(3)-Au(1) 125.3(3) C(18)-N(2)-C(1) 128.4(4) C(4)-N(1)-C(1) 106.8(4) C(4)-N(1)-Au(1) 130.3(3) C(1)-N(1)-Au(1) 114.3(3) C(72)-C(71)-C(76) 118.5(5) C(72)-C(71)-C(61) 121.8(5) C(76)-C(71)-C(61) 119.7(5) C(9)-C(10)-C(5) 120.1(5) O(1)-C(8)-C(7) 124.2(5) O(1)-C(8)-C(9) 116.1(5)

316

C(7)-C(8)-C(9) 119.8(5) C(10)-C(9)-C(8) 121.3(5) C(8)-C(7)-C(6) 118.3(5) C(25)-O(2)-C(28) 117.2(4) C(14)-C(13)-C(12) 121.6(6) C(58)-C(59)-C(54) 119.5(5) C(55)-C(54)-C(59) 118.4(5) C(55)-C(54)-C(44) 121.5(5) C(59)-C(54)-C(44) 120.0(5) C(72)-C(73)-C(74) 120.4(6) C(73)-C(72)-C(71) 121.0(6) C(75)-C(76)-C(71) 119.7(6) C(75)-C(74)-C(73) 118.6(6) C(76)-C(75)-C(74) 121.8(6) C(32)-C(31)-C(30) 119.2(5) C(8)-O(1)-C(11) 117.8(5) C(38)-C(39)-C(40) 119.0(6) C(78)-C(79)-C(80) 120.7(6) C(57)-C(58)-C(59) 120.9(6) C(58)-C(57)-C(56) 120.8(5) C(56)-C(55)-C(54) 120.0(6) C(57)-C(56)-C(55) 120.3(6)

317

24. X-Ray crystallographic data for (PPhMe2Au)LcBr2

Table AI-24a. Crystallographic data for Table AI-24b. Data collection

ND113009

C42H35AuBr2N3O2P Bruker SMART CCD area-detector

Mr = 1001.49 diffractometer

Monoclinic, P21/c  scans

a = 10.726(2) Å Absorption correction: multi-scan

b = 16.066(4) Å Tmin = 0.2363, Tmax = 0.7062

c = 21.324(5) Å 42807 measured reflections

α = 90.00 º 8320 independent reflections

 = 98.766(2) º 7222 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0370

3 V = 3631.8(14) Å  max = 27.50º

Z = 4 h = -13  13

-3 Dx = 1.832 Mg m k = -20  20

Mo K radiation l = -27 27

Cell parameters from 9837 reflections

 = 1.59±27.50º

 = 6.337 mm-1

T = 170(2) K

irregular, red

0.32  0.16 0.06 mm

318

Table AI-24c. Refinement Figure AI-24a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0238 wR(F2) = 0.0573

S = 1.031

8320 reflections

464 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0279P) + 4.2036P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.093

-3 max = 1.832 eÅ

-3 min = -0.980 eÅ

Table AI-24d. Selected geometric parameters (Å, º). Au(1)-N(1) 2.113(2) N(1)-Au(1)-P(1) 160.00(7) Au(1)-P(1) 2.2179(8) N(1)-Au(1)-N(3) 82.44(8) Au(1)-N(3) 2.560(2) P(1)-Au(1)-N(3) 117.44(6) Br(1)-C(3) 1.886(3) C(4)-N(1)-C(1) 106.7(2) Br(2)-C(20) 1.877(3) C(4)-N(1)-Au(1) 123.03(19) N(1)-C(4) 1.356(4) C(1)-N(1)-Au(1) 127.64(18) N(1)-C(1) 1.393(3) C(18)-N(2)-C(1) 131.1(2) N(2)-C(18) 1.309(4) C(21)-N(3)-C(18) 106.0(2) N(2)-C(1) 1.328(4) C(21)-N(3)-Au(1) 132.82(19) N(3)-C(21) 1.327(4) C(18)-N(3)-Au(1) 115.88(17) N(3)-C(18) 1.390(4) C(13)-C(12)-C(11) 121.0(3) C(12)-C(13) 1.379(4) N(1)-C(4)-C(3) 109.5(2) C(12)-C(11) 1.402(4) N(1)-C(4)-C(5) 122.4(3) C(4)-C(3) 1.415(4) C(3)-C(4)-C(5) 128.1(3) C(4)-C(5) 1.464(4) C(19)-C(20)-C(21) 108.0(2) C(20)-C(19) 1.359(4) C(19)-C(20)-Br(2) 124.9(2) C(20)-C(21) 1.444(4) C(21)-C(20)-Br(2) 126.3(2)

319

C(3)-C(2) 1.381(4) C(2)-C(3)-C(4) 109.1(2) C(11)-C(16) 1.388(4) C(2)-C(3)-Br(1) 125.8(2) C(11)-C(2) 1.469(4) C(4)-C(3)-Br(1) 125.1(2) C(2)-C(1) 1.436(4) C(16)-C(11)-C(12) 117.3(3) C(13)-C(14) 1.389(4) C(16)-C(11)-C(2) 120.5(3) C(14)-O(1) 1.365(3) C(12)-C(11)-C(2) 122.2(3) C(14)-C(15) 1.388(4) C(3)-C(2)-C(1) 104.6(2) C(5)-C(10) 1.393(4) C(3)-C(2)-C(11) 130.0(3) C(5)-C(6) 1.395(4) C(1)-C(2)-C(11) 125.4(3) C(16)-C(15) 1.388(4) C(12)-C(13)-C(14) 120.7(3) C(10)-C(9) 1.382(5) O(1)-C(14)-C(15) 124.2(3) C(9)-C(8) 1.367(6) O(1)-C(14)-C(13) 116.3(3) C(21)-C(22) 1.472(4) C(15)-C(14)-C(13) 119.5(3) C(6)-C(7) 1.382(4) N(2)-C(1)-N(1) 128.8(2) C(18)-C(19) 1.456(4) N(2)-C(1)-C(2) 121.1(2) C(19)-C(28) 1.468(4) N(1)-C(1)-C(2) 110.1(2) C(8)-C(7) 1.375(5) C(10)-C(5)-C(6) 117.7(3) C(30)-C(29) 1.375(4) C(10)-C(5)-C(4) 121.7(3) C(30)-C(31) 1.387(4) C(6)-C(5)-C(4) 120.6(3) C(31)-O(2) 1.372(4) C(15)-C(16)-C(11) 122.4(3) C(31)-C(32) 1.384(4) C(9)-C(10)-C(5) 121.1(3) C(33)-C(28) 1.381(4) C(16)-C(15)-C(14) 119.1(3) C(33)-C(32) 1.394(4) C(8)-C(9)-C(10) 120.2(3) C(28)-C(29) 1.401(4) N(3)-C(21)-C(20) 110.9(2) C(36)-C(37) 1.381(5) N(3)-C(21)-C(22) 122.1(3) C(36)-C(35) 1.385(4) C(20)-C(21)-C(22) 126.9(3) C(35)-C(40) 1.390(5) C(7)-C(6)-C(5) 120.8(3) C(35)-P(1) 1.810(3) N(2)-C(18)-N(3) 129.1(3) C(40)-C(39) 1.386(5) N(2)-C(18)-C(19) 120.2(2) C(39)-C(38) 1.366(5) N(3)-C(18)-C(19) 110.5(2) C(37)-C(38) 1.369(5) C(20)-C(19)-C(18) 104.4(2) C(26)-C(25) 1.380(5) C(20)-C(19)-C(28) 131.2(3) C(26)-C(27) 1.386(4) C(18)-C(19)-C(28) 124.2(3) C(23)-C(24) 1.388(4) C(9)-C(8)-C(7) 120.1(3) C(23)-C(22) 1.398(4) C(8)-C(7)-C(6) 120.2(3) C(24)-C(25) 1.382(5) C(29)-C(30)-C(31) 120.2(3) C(22)-C(27) 1.392(4) O(2)-C(31)-C(32) 125.2(3) C(17)-O(1) 1.417(4) O(2)-C(31)-C(30) 115.0(3) C(34)-O(2) 1.410(4) C(32)-C(31)-C(30) 119.8(3) C(42)-P(1) 1.811(3) C(28)-C(33)-C(32) 121.6(3) C(41)-P(1) 1.816(3) C(33)-C(28)-C(29) 117.9(3) C(33)-C(28)-C(19) 123.6(3) C(29)-C(28)-C(19) 118.4(3) C(31)-C(32)-C(33) 119.4(3)

320

C(30)-C(29)-C(28) 121.0(3) C(37)-C(36)-C(35) 121.0(3) C(36)-C(35)-C(40) 117.9(3) C(36)-C(35)-P(1) 121.9(2) C(40)-C(35)-P(1) 120.1(2) C(39)-C(40)-C(35) 120.6(3) C(38)-C(39)-C(40) 120.4(3) C(38)-C(37)-C(36) 120.4(3) C(25)-C(26)-C(27) 119.8(3) C(24)-C(23)-C(22) 119.8(3) C(25)-C(24)-C(23) 120.4(3) C(26)-C(25)-C(24) 120.2(3) C(27)-C(22)-C(23) 119.0(3) C(27)-C(22)-C(21) 119.8(3) C(23)-C(22)-C(21) 121.2(3) C(26)-C(27)-C(22) 120.7(3) C(39)-C(38)-C(37) 119.7(3) C(35)-P(1)-C(42) 105.57(15) C(35)-P(1)-C(41) 102.48(15) C(42)-P(1)-C(41) 105.06(16) C(35)-P(1)-Au(1) 112.92(10) C(42)-P(1)-Au(1) 112.48(11) C(41)-P(1)-Au(1) 117.17(11) C(14)-O(1)-C(17) 117.7(3) C(31)-O(2)-C(34) 118.1(3)

321

25. X-Ray crystallographic data for Zn azadipyrromethene complex

Table AI-25a. Crystallographic data for Table AI-25b. Data collection

ND110409

C67H47N6O6Zn3·2(C3H6O) Bruker SMART CCD area-detector

Mr = 1344.37 diffractometer

Monoclinic, Pc  scans

a = 9.8105(12) Å Absorption correction: multi-scan

b = 9.6680(12) Å Tmin = 0.5942, Tmax = 0.8540

c = 31.534(4) Å 33219 measured reflections

α = 90.00 º 13138 independent reflections

 = 94.371(2) º 10465 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0443

3 V = 2982.2(6) Å  max = 27.40º

Z = 2 h = -12  12

-3 Dx = 1.497 Mg m k = -12  12

Mo K radiation l = -40 40

Cell parameters from 9931 reflections

 = 1.30±27.40º

 = 1.263 mm-1

T = 170 (2) K

Irregular, red

0.446 0.15 0.13 mm

322

Table AI-25c. Refinement Figure AI-25a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms and solvent molecules are

omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0413 wR(F2) = 0.0888

S = 1.006

13138 reflections

818 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0519 P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.107

-3 max = 0.445 eÅ

-3 min = -0.629 eÅ

Table AI-25d. Selected geometric parameters (Å, º). Zn1-O4 1.934(3) O4-Zn1-O2 119.86(13) Zn1-O2 1.938(3) O4-Zn1-O1 131.33(13) Zn1-O1 1.949(3) O2-Zn1-O1 84.82(12) Zn1-O3 1.949(3) O4-Zn1-O3 82.86(11) Zn1-Zn2 3.0003(7) O2-Zn1-O3 132.03(13) Zn1-Zn3 3.0195(7) O1-Zn1-O3 112.35(13) Zn2-N1 1.969(3) O4-Zn1-Zn2 137.64(8) Zn2-N3 1.969(3) O2-Zn1-Zn2 42.61(8) Zn2-O5 2.043(3) O1-Zn1-Zn2 42.53(8)

323

Zn2-O1 2.045(3) O3-Zn1-Zn2 139.19(9) Zn2-O2 2.049(3) O4-Zn1-Zn3 41.87(8) Zn3-N4 1.970(3) O2-Zn1-Zn3 144.81(9) Zn3-N6 1.971(3) O1-Zn1-Zn3 130.32(9) Zn3-O3 2.017(3) O3-Zn1-Zn3 41.26(8) Zn3-O4 2.040(3) Zn2-Zn1-Zn3 172.33(2) Zn3-O6 2.109(3) N1-Zn2-N3 91.78(13) O3-C42 1.338(5) N1-Zn2-O5 110.95(15) O4-C58 1.331(5) N3-Zn2-O5 107.59(13) O2-C22 1.341(5) N1-Zn2-O1 88.50(12) O1-C10 1.333(5) N3-Zn2-O1 155.93(13) O6-C65 1.224(5) O5-Zn2-O1 94.71(13) N6-C36 1.341(5) N1-Zn2-O2 147.60(13) N6-C33 1.379(5) N3-Zn2-O2 87.49(12) N1-C4 1.354(5) O5-Zn2-O2 100.06(14) N1-C1 1.373(5) O1-Zn2-O2 79.61(11) N2-C1 1.321(5) N1-Zn2-Zn1 124.48(9) N2-C17 1.327(5) N3-Zn2-Zn1 125.83(9) N3-C20 1.342(5) O5-Zn2-Zn1 95.90(9) N3-C17 1.385(5) O1-Zn2-Zn1 40.10(8) N4-C52 1.334(5) O2-Zn2-Zn1 39.80(8) N4-C49 1.374(5) N4-Zn3-N6 91.91(13) N5-C49 1.322(5) N4-Zn3-O3 152.21(13) N5-C33 1.337(5) N6-Zn3-O3 88.81(12) C36-C35 1.421(5) N4-Zn3-O4 88.54(13) C36-C37 1.456(6) N6-Zn3-O4 152.91(13) C34-C35 1.357(6) O3-Zn3-O4 78.60(11) C34-C33 1.426(6) N4-Zn3-O6 102.86(13) C34-C43 1.483(5) N6-Zn3-O6 108.61(12) C19-C18 1.383(6) O3-Zn3-O6 103.20(13) C19-C20 1.420(6) O4-Zn3-O6 97.66(12) C23-C24 1.368(7) N4-Zn3-Zn1 125.25(10) C23-C22 1.393(6) N6-Zn3-Zn1 125.98(10) C5-C6 1.405(6) O3-Zn3-Zn1 39.60(8) C5-C10 1.420(6) O4-Zn3-Zn1 39.26(8) C5-C4 1.442(6) O6-Zn3-Zn1 100.08(8) C3-C2 1.378(6) C42-O3-Zn1 132.9(2) C3-C4 1.422(6) C42-O3-Zn3 127.6(2) C22-C21 1.406(6) Zn1-O3-Zn3 99.14(12) C53-C54 1.400(6) C58-O4-Zn1 133.1(3) C53-C58 1.416(6) C58-O4-Zn3 128.0(3) C53-C52 1.455(6) Zn1-O4-Zn3 98.87(12) C20-C21 1.449(6) C22-O2-Zn1 133.9(2) C17-C18 1.441(5) C22-O2-Zn2 127.1(2)

324

C58-C57 1.392(6) Zn1-O2-Zn2 97.58(12) C11-C16 1.372(6) C10-O1-Zn1 134.9(3) C11-C12 1.400(6) C10-O1-Zn2 127.7(2) C11-C2 1.466(6) Zn1-O1-Zn2 97.37(13) C1-C2 1.438(6) C65-O6-Zn3 138.7(3) C39-C38 1.365(6) C36-N6-C33 108.4(3) C39-C40 1.380(6) C36-N6-Zn3 127.9(3) C10-C9 1.389(6) C33-N6-Zn3 123.7(3) C26-C25 1.353(6) C4-N1-C1 107.9(3) C26-C21 1.413(6) C4-N1-Zn2 128.5(3) C54-C55 1.367(6) C1-N1-Zn2 122.8(3) C13-C14 1.371(7) C1-N2-C17 125.9(3) C13-C12 1.376(6) C20-N3-C17 107.9(3) C24-C25 1.366(7) C20-N3-Zn2 128.8(3) C38-C37 1.403(6) C17-N3-Zn2 122.8(3) C40-C41 1.347(6) C52-N4-C49 108.3(3) C59-C64 1.382(7) C52-N4-Zn3 128.3(3) C59-C60 1.390(7) C49-N4-Zn3 123.2(3) C59-C50 1.472(6) C49-N5-C33 126.3(3) C27-C32 1.369(6) N6-C36-C35 108.9(3) C27-C28 1.386(6) N6-C36-C37 123.9(3) C27-C18 1.470(5) C35-C36-C37 127.1(4) C55-C56 1.350(7) C35-C34-C33 107.0(4) C52-C51 1.420(6) C35-C34-C43 125.9(4) C49-C50 1.446(6) C33-C34-C43 127.1(4) C42-C41 1.403(6) C18-C19-C20 107.6(4) C42-C37 1.408(5) C24-C23-C22 121.9(4) C30-C29 1.363(6) C6-C5-C10 116.5(4) C30-C31 1.363(7) C6-C5-C4 117.5(4) C51-C50 1.358(6) C10-C5-C4 126.0(4) C57-C56 1.373(7) C2-C3-C4 107.9(4) C9-C8 1.362(7) N5-C33-N6 126.0(3) C7-C6 1.368(6) N5-C33-C34 125.7(4) C7-C8 1.381(7) N6-C33-C34 108.0(3) C60-C61 1.378(7) O2-C22-C23 119.1(4) C64-C63 1.401(7) O2-C22-C21 122.4(4) C48-C47 1.382(7) C23-C22-C21 118.5(4) C48-C43 1.386(6) C54-C53-C58 116.6(4) C32-C31 1.372(7) C54-C53-C52 118.7(4) C63-C62 1.357(8) C58-C53-C52 124.7(4) C14-C15 1.366(7) N3-C20-C19 109.9(3) C44-C45 1.386(7) N3-C20-C21 122.9(4) C44-C43 1.387(6) C19-C20-C21 127.1(4) C46-C47 1.347(7) N2-C17-N3 126.1(3)

325

C46-C45 1.368(8) N2-C17-C18 125.0(3) C16-C15 1.391(7) N3-C17-C18 108.7(3) C61-C62 1.375(8) O4-C58-C57 119.0(4) C28-C29 1.359(6) O4-C58-C53 122.2(4) C65-C71 1.455(7) C57-C58-C53 118.7(4) C65-C66 1.483(6) C16-C11-C12 118.6(4) O9-C67 1.198(6) C16-C11-C2 121.2(4) C72-C67 1.478(8) C12-C11-C2 120.2(4) C67-C68 1.490(8) N2-C1-N1 127.5(4) O12-C69 1.203(6) N2-C1-C2 123.3(4) C73-C69 1.490(8) N1-C1-C2 109.2(3) C69-C70 1.471(8) C38-C39-C40 120.0(4) O1-C10-C9 119.1(4) O1-C10-C5 122.0(4) C9-C10-C5 118.9(4) C34-C35-C36 107.7(4) C25-C26-C21 122.7(4) C55-C54-C53 123.4(4) C14-C13-C12 120.5(5) C25-C24-C23 120.2(4) C39-C38-C37 122.3(4) C22-C21-C26 117.3(4) C22-C21-C20 125.1(4) C26-C21-C20 117.5(4) C41-C40-C39 119.2(4) C64-C59-C60 118.8(4) C64-C59-C50 120.2(4) C60-C59-C50 121.0(4) C32-C27-C28 116.6(4) C32-C27-C18 121.0(4) C28-C27-C18 122.3(4) C56-C55-C54 119.0(4) N1-C4-C3 109.2(3) N1-C4-C5 122.6(4) C3-C4-C5 128.1(4) C13-C12-C11 120.0(4) N4-C52-C51 109.7(4) N4-C52-C53 123.6(4) C51-C52-C53 126.6(4) N5-C49-N4 126.9(4) N5-C49-C50 124.8(4) N4-C49-C50 108.1(3) C26-C25-C24 119.4(4) O3-C42-C41 119.2(3)

326

O3-C42-C37 122.2(3) C41-C42-C37 118.6(4) C19-C18-C17 105.8(3) C19-C18-C27 126.8(4) C17-C18-C27 127.4(4) C38-C37-C42 117.2(4) C38-C37-C36 118.5(4) C42-C37-C36 124.3(4) C29-C30-C31 117.8(4) C50-C51-C52 107.7(4) C51-C50-C49 106.2(4) C51-C50-C59 126.9(4) C49-C50-C59 126.9(4) C40-C41-C42 122.7(4) C56-C57-C58 121.5(4) C3-C2-C1 105.7(4) C3-C2-C11 127.7(4) C1-C2-C11 126.5(4) C8-C9-C10 122.2(5) C6-C7-C8 118.3(5) C9-C8-C7 120.3(5) C61-C60-C59 120.5(5) C59-C64-C63 119.8(5) C47-C48-C43 120.3(5) C7-C6-C5 123.7(4) C27-C32-C31 121.3(5) C62-C63-C64 120.6(5) C55-C56-C57 120.7(4) C15-C14-C13 120.2(5) C45-C44-C43 121.0(5) C47-C46-C45 119.2(4) C11-C16-C15 120.9(5) C48-C43-C44 117.5(4) C48-C43-C34 123.9(4) C44-C43-C34 118.6(4) C62-C61-C60 120.5(5) C29-C28-C27 121.7(4) C46-C47-C48 121.7(5) C28-C29-C30 121.2(5) C30-C31-C32 121.4(5) C14-C15-C16 119.7(5) C46-C45-C44 120.3(5) C63-C62-C61 119.8(5) O6-C65-C71 122.2(4)

327

O6-C65-C66 119.8(4) C71-C65-C66 118.0(4) O9-C67-C72 121.6(6) O9-C67-C68 121.0(5) C72-C67-C68 117.4(6) O12-C69-C70 121.6(5) O12-C69-C73 121.9(5) C70-C69-C73 116.4(5)

328

26. X-Ray crystallographic data for Vanadyl azadipyrromethene complex

Table AI-26a. Crystallographic data for Table AI-26b. Data collection

ND040610

C40H40N4O4V Bruker SMART CCD area-detector

Mr = 691.70 diffractometer

Monoclinic, P21/n  scans

a = 20.5210(17) Å Absorption correction: multi-scan

b = 7.5236(6) Å Tmin = 0.9032, Tmax = 0.9409

c = 21.7849(18) Å 31730 measured reflections

α = 90.00 º 5842 independent reflections

 = 99.3420(10) º 4384 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0487

3 V = 3318.8(5) Å  max = 25.00º

Z = 4 h = -24  24

-3 Dx = 1.384 Mg m k = -8  8

Mo K radiation l = -25 25

Cell parameters from 5516 reflections

 = 1.26±25.00º

 = 0.350 mm-1

T = 170 (2) K

Irregular, metallic red

0.30 0.24 0.18 mm

329

Table AI-26c. Refinement Figure AI-26a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity. Solvent

molecules are not shown for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0472 wR(F2) = 0.1309

S = 1.046

5842 reflections

452 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0849 P) + 12.7507P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.108

-3 max = 0.663 eÅ

-3 min = -0.361 eÅ

Table AI-26d. Selected geometric parameters (Å, º). V(1)-O(1) 1.618(2) O(1)-V(1)-O(2) 107.57(10) V(1)-O(2) 1.927(2) O(1)-V(1)-O(3) 113.06(10) V(1)-O(3) 1.945(2) O(2)-V(1)-O(3) 81.67(9) V(1)-N(1) 2.016(2) O(1)-V(1)-N(1) 105.04(10) V(1)-N(3) 2.037(2) O(2)-V(1)-N(1) 86.43(9) N(1)-C(4) 1.373(4) O(3)-V(1)-N(1) 141.90(9) N(1)-C(1) 1.390(4) O(1)-V(1)-N(3) 105.98(10) N(3)-C(20) 1.361(4) O(2)-V(1)-N(3) 146.45(10) N(3)-C(17) 1.407(4) O(3)-V(1)-N(3) 84.85(9) N(2)-C(17) 1.317(4) N(1)-V(1)-N(3) 85.50(10) N(2)-C(1) 1.339(4) C(4)-N(1)-C(1) 106.3(2) C(21)-C(26) 1.404(4) C(4)-N(1)-V(1) 125.6(2) C(21)-C(22) 1.416(4) C(1)-N(1)-V(1) 127.22(19) C(21)-C(20) 1.442(4) C(20)-N(3)-C(17) 106.4(2) C(1)-C(2) 1.431(4) C(20)-N(3)-V(1) 125.69(19)

330

C(17)-C(18) 1.457(4) C(17)-N(3)-V(1) 126.64(19) C(5)-C(10) 1.410(5) C(17)-N(2)-C(1) 123.9(3) C(5)-C(6) 1.413(4) C(26)-C(21)-C(22) 118.3(3) C(5)-C(4) 1.453(4) C(26)-C(21)-C(20) 121.9(3) C(10)-O(2) 1.338(4) C(22)-C(21)-C(20) 119.8(3) C(10)-C(9) 1.400(5) N(2)-C(1)-N(1) 126.9(3) C(4)-C(3) 1.405(4) N(2)-C(1)-C(2) 123.6(3) C(20)-C(19) 1.426(4) N(1)-C(1)-C(2) 109.5(3) C(9)-C(8) 1.379(5) N(2)-C(17)-N(3) 125.8(3) C(18)-C(19) 1.364(4) N(2)-C(17)-C(18) 125.0(3) C(18)-C(27) 1.471(4) N(3)-C(17)-C(18) 109.1(2) C(24)-C(25) 1.376(4) C(10)-C(5)-C(6) 118.3(3) C(24)-C(23) 1.386(5) C(10)-C(5)-C(4) 121.9(3) C(26)-O(3) 1.345(3) C(6)-C(5)-C(4) 119.8(3) C(26)-C(25) 1.399(4) O(2)-C(10)-C(9) 118.6(3) C(27)-C(32) 1.388(5) O(2)-C(10)-C(5) 122.4(3) C(27)-C(28) 1.395(5) C(9)-C(10)-C(5) 119.0(3) C(3)-C(2) 1.375(4) N(1)-C(4)-C(3) 109.9(3) C(2)-C(11) 1.460(4) N(1)-C(4)-C(5) 122.9(3) C(32)-C(31) 1.369(5) C(3)-C(4)-C(5) 127.1(3) C(6)-C(7) 1.366(5) N(3)-C(20)-C(19) 110.1(3) C(22)-C(23) 1.368(4) N(3)-C(20)-C(21) 123.8(3) C(8)-C(7) 1.394(5) C(19)-C(20)-C(21) 126.1(3) C(11)-C(16) 1.383(5) C(8)-C(9)-C(10) 121.2(3) C(11)-C(12) 1.389(5) C(19)-C(18)-C(17) 105.6(3) C(28)-C(29) 1.391(5) C(19)-C(18)-C(27) 126.1(3) C(30)-C(31) 1.370(6) C(17)-C(18)-C(27) 128.4(3) C(30)-C(29) 1.373(6) C(25)-C(24)-C(23) 120.2(3) C(12)-C(13) 1.367(5) C(18)-C(19)-C(20) 108.8(3) C(13)-C(14) 1.349(6) O(3)-C(26)-C(25) 118.0(3) C(15)-C(14) 1.378(6) O(3)-C(26)-C(21) 122.5(3) C(15)-C(16) 1.390(5) C(25)-C(26)-C(21) 119.4(3) C(33)-O(4) 1.379(6) C(32)-C(27)-C(28) 116.8(3) C(33)-C(34) 1.513(7) C(32)-C(27)-C(18) 120.1(3) O(4)-C(36) 1.341(6) C(28)-C(27)-C(18) 122.9(3) C(36)-C(35) 1.471(7) C(2)-C(3)-C(4) 108.2(3) C(34)-C(35) 1.538(7) C(3)-C(2)-C(1) 106.1(3) C(39)-N(4) 1.487(5) C(3)-C(2)-C(11) 125.9(3) C(39)-C(40) 1.502(5) C(1)-C(2)-C(11) 128.0(3) C(37)-C(38) 1.520(6) C(24)-C(25)-C(26) 120.9(3) C(38)-N(4) 1.490(4) C(31)-C(32)-C(27) 121.8(3) C(7)-C(6)-C(5) 121.8(3) C(23)-C(22)-C(21) 121.3(3) C(9)-C(8)-C(7) 120.1(3)

331

C(6)-C(7)-C(8) 119.6(3) C(16)-C(11)-C(12) 117.5(3) C(16)-C(11)-C(2) 122.8(3) C(12)-C(11)-C(2) 119.6(3) C(22)-C(23)-C(24) 119.9(3) C(29)-C(28)-C(27) 121.2(4) C(31)-C(30)-C(29) 119.1(4) C(32)-C(31)-C(30) 120.8(3) C(30)-C(29)-C(28) 120.2(4) C(13)-C(12)-C(11) 122.5(4) C(14)-C(13)-C(12) 119.1(4) C(14)-C(15)-C(16) 119.9(4) C(11)-C(16)-C(15) 120.1(4) C(13)-C(14)-C(15) 120.8(4) C(26)-O(3)-V(1) 129.00(18) C(10)-O(2)-V(1) 127.05(19) O(4)-C(33)-C(34) 107.6(4) C(36)-O(4)-C(33) 113.0(4) O(4)-C(36)-C(35) 111.0(5) C(33)-C(34)-C(35) 104.2(4) C(36)-C(35)-C(34) 104.0(4) N(4)-C(39)-C(40) 111.1(3) N(4)-C(38)-C(37) 110.4(3) C(39)-N(4)-C(38) 114.3(3)

332

27. X-Ray crystallographic data for Mn azadipyrromethene complex

Table AI-27a. Crystallographic data for Table AI-27b. Data collection

ND031710

C72H42Mn2N6O6 Bruker SMART CCD area-detector

Mr = 1197.00 diffractometer

Monoclinic, P21/c  scans

a = 11.337(2) Å Absorption correction: multi-scan

b = 25.069(4) Å Tmin = 0.8906, Tmax = 0.9858

c = 11.176(2) Å 27871 measured reflections

α = 90.00 º 4944 independent reflections

 = 117.931(2) º 2962 reflections with I > 2(I)

γ = 90.00 º Rint = 0.1143

3 V = 2806.3(9) Å  max = 25.00º

Z = 2 h = -13  13

-3 Dx = 1.417 Mg m k = -29  29

Mo K radiation l = -13 13

Cell parameters from 1440 reflections

 = 2.03±25.00º

 = 0.514 mm-1

T = 170 (2) K

Irregular, black

0.23 0.20 0.03 mm

333

Table AI-27c. Refinement Figure AI-27a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity. One

phenyl ring on the ligand is disordered, which is

not shown for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0552 wR(F2) = 0.1260

S = 0.672

4944 reflections

442 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.0657 P) + 1.3490P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.070

-3 max = 0.444 eÅ

-3 min = -0.471 eÅ

Table AI-27d. Selected geometric parameters (Å, º). Mn(1)-O(1) 1.859(3) O(1)-Mn(1)-O(2) 90.95(11) Mn(1)-O(2) 1.911(3) O(1)-Mn(1)-N(3) 91.24(13) Mn(1)-N(3) 1.943(3) O(2)-Mn(1)-N(3) 169.85(12) Mn(1)-N(1) 1.951(3) O(1)-Mn(1)-N(1) 176.23(13) Mn(1)-O(2)#1 2.321(3) O(2)-Mn(1)-N(1) 89.34(12) Mn(1)-O(3) 2.353(3) N(3)-Mn(1)-N(1) 89.13(14) O(2)-C(22) 1.353(4) O(1)-Mn(1)-O(2)#1 92.49(11) O(2)-Mn(1)#1 2.321(3) O(2)-Mn(1)-O(2)#1 79.29(11) O(1)-C(10) 1.334(5) N(3)-Mn(1)-O(2)#1 90.70(11) O(3)-C(33) 1.441(5) N(1)-Mn(1)-O(2)#1 91.25(11) O(3)-C(36) 1.450(5) O(1)-Mn(1)-O(3) 87.17(11) N(1)-C(20) 1.360(5) O(2)-Mn(1)-O(3) 90.80(11) N(1)-C(17) 1.385(5) N(3)-Mn(1)-O(3) 99.21(12) N(3)-C(4) 1.366(5) N(1)-Mn(1)-O(3) 89.07(12)

334

N(3)-C(1) 1.389(5) O(2)#1-Mn(1)-O(3) 170.09(10) N(2)-C(1) 1.316(5) C(22)-O(2)-Mn(1) 124.3(2) N(2)-C(17) 1.330(5) C(22)-O(2)-Mn(1)#1 115.8(2) C(23)-C(24) 1.370(6) Mn(1)-O(2)-Mn(1)#1 100.71(11) C(23)-C(22) 1.387(5) C(10)-O(1)-Mn(1) 130.4(3) C(10)-C(5) 1.404(5) C(33)-O(3)-C(36) 108.0(3) C(10)-C(9) 1.408(6) C(33)-O(3)-Mn(1) 115.8(3) C(4)-C(3) 1.420(6) C(36)-O(3)-Mn(1) 130.4(3) C(4)-C(5) 1.430(6) C(20)-N(1)-C(17) 107.7(3) C(22)-C(21) 1.417(6) C(20)-N(1)-Mn(1) 125.8(3) C(17)-C(18) 1.442(6) C(17)-N(1)-Mn(1) 126.4(3) C(19)-C(18) 1.371(6) C(4)-N(3)-C(1) 107.2(3) C(19)-C(20) 1.411(5) C(4)-N(3)-Mn(1) 126.6(3) C(20)-C(21) 1.439(6) C(1)-N(3)-Mn(1) 125.1(3) C(26)-C(25) 1.378(6) C(1)-N(2)-C(17) 123.4(3) C(26)-C(21) 1.406(6) C(24)-C(23)-C(22) 120.4(4) C(9)-C(8) 1.358(6) O(1)-C(10)-C(5) 122.9(4) C(1)-C(2) 1.449(6) O(1)-C(10)-C(9) 118.1(4) C(3)-C(2) 1.362(6) C(5)-C(10)-C(9) 119.0(4) C(25)-C(24) 1.386(6) N(3)-C(4)-C(3) 109.4(4) C(5)-C(6) 1.422(6) N(3)-C(4)-C(5) 123.1(4) C(18)-C(27) 1.476(6) C(3)-C(4)-C(5) 127.5(4) C(6)-C(7) 1.353(6) O(2)-C(22)-C(23) 118.2(4) C(7)-C(8) 1.397(6) O(2)-C(22)-C(21) 121.3(3) C(2)-C(11) 1.476(6) C(23)-C(22)-C(21) 120.4(4) C(11)-C(12A) 1.307(10) N(2)-C(17)-N(1) 126.0(4) C(11)-C(15A) 1.307(10) N(2)-C(17)-C(18) 125.4(4) C(11)-C(16) 1.484(10) N(1)-C(17)-C(18) 108.6(4) C(11)-C(12) 1.503(10) C(18)-C(19)-C(20) 108.6(4) C(14)-C(14A) 1.236(13) N(1)-C(20)-C(19) 109.3(4) C(14)-C(13A) 1.362(12) N(1)-C(20)-C(21) 123.2(4) C(14)-C(15) 1.452(13) C(19)-C(20)-C(21) 127.5(4) C(14)-C(13) 1.518(12) C(25)-C(26)-C(21) 122.1(4) C(16)-C(15) 1.406(13) C(8)-C(9)-C(10) 121.3(4) C(12)-C(13) 1.429(13) C(26)-C(21)-C(22) 117.0(4) C(27)-C(32) 1.274(13) C(26)-C(21)-C(20) 120.8(4) C(27)-C(28) 1.364(7) C(22)-C(21)-C(20) 122.2(4) C(27)-C(32A) 1.557(13) N(2)-C(1)-N(3) 127.3(4) C(36)-C(35) 1.504(6) N(2)-C(1)-C(2) 124.0(4) C(33)-C(34) 1.500(7) N(3)-C(1)-C(2) 108.7(4) C(35)-C(34) 1.502(7) C(2)-C(3)-C(4) 108.6(4) C(12A)-C(13A) 1.425(12) C(26)-C(25)-C(24) 119.1(4) C(15A)-C(14A) 1.428(15) C(10)-C(5)-C(6) 117.9(4) C(30)-C(31) 1.155(13) C(10)-C(5)-C(4) 122.6(4)

335

C(30)-C(29) 1.319(9) C(6)-C(5)-C(4) 119.5(4) C(30)-C(31A) 1.697(15) C(19)-C(18)-C(17) 105.9(4) C(29)-C(28) 1.389(7) C(19)-C(18)-C(27) 126.2(4) C(31A)-C(32A) 1.392(18) C(17)-C(18)-C(27) 127.9(4) C(31)-C(32) 1.408(18) C(23)-C(24)-C(25) 120.9(4) C(7)-C(6)-C(5) 121.7(4) C(6)-C(7)-C(8) 119.8(4) C(9)-C(8)-C(7) 120.2(4) C(3)-C(2)-C(1) 106.1(4) C(3)-C(2)-C(11) 127.5(4) C(1)-C(2)-C(11) 126.4(4) C(12A)-C(11)-C(15A) 88.2(7) C(12A)-C(11)-C(2) 120.7(5) C(15A)-C(11)-C(2) 120.4(6) C(12A)-C(11)-C(16) 119.8(6) C(15A)-C(11)-C(16) 51.4(6) C(2)-C(11)-C(16) 118.2(5) C(12A)-C(11)-C(12) 59.2(6) C(15A)-C(11)-C(12) 120.2(7) C(2)-C(11)-C(12) 119.4(5) C(16)-C(11)-C(12) 100.8(5) C(14A)-C(14)-C(13A) 89.1(9) C(14A)-C(14)-C(15) 49.0(7) C(13A)-C(14)-C(15) 119.2(7) C(14A)-C(14)-C(13) 119.7(7) C(13A)-C(14)-C(13) 59.5(6) C(15)-C(14)-C(13) 100.7(7) C(15)-C(16)-C(11) 117.7(8) C(16)-C(15)-C(14) 119.3(9) C(13)-C(12)-C(11) 116.8(8) C(12)-C(13)-C(14) 117.5(9) C(32)-C(27)-C(28) 108.5(7) C(32)-C(27)-C(18) 125.2(7) C(28)-C(27)-C(18) 124.0(5) C(32)-C(27)-C(32A) 31.0(6) C(28)-C(27)-C(32A) 122.6(6) C(18)-C(27)-C(32A) 112.0(6) O(3)-C(36)-C(35) 105.1(4) O(3)-C(33)-C(34) 107.1(4) C(34)-C(35)-C(36) 102.2(4) C(33)-C(34)-C(35) 105.3(4) C(11)-C(12A)-C(13A) 122.3(9) C(14)-C(13A)-C(12A) 120.1(9) C(11)-C(15A)-C(14A) 120.9(10)

336

C(14)-C(14A)-C(15A) 124.7(10) C(31)-C(30)-C(29) 115.8(9) C(31)-C(30)-C(31A) 32.4(8) C(29)-C(30)-C(31A) 119.9(7) C(30)-C(29)-C(28) 120.1(7) C(27)-C(28)-C(29) 122.5(6) C(32A)-C(31A)-C(30) 115.0(11) C(31A)-C(32A)-C(27) 115.4(11) C(30)-C(31)-C(32) 122.7(12) C(27)-C(32)-C(31) 125.8(11)

337

28. X-Ray crystallographic data for Fe azadipyrromethene complex

Table AI-28a. Crystallographic data for Table AI-28b. Data collection

ND111609

C72H56Fe2N6O6 Bruker SMART CCD area-detector

Mr = 1212.93 diffractometer

Monoclinic, P21/n  scans

a = 11.6807(17) Å Absorption correction: multi-scan

b = 9.1254(13) Å Tmin = 0.8323, Tmax = 0.9510

c = 30.033(5) Å 36879 measured reflections

α = 90.00 º 7204 independent reflections

 = 100.249(2) º 5546 reflections with I > 2(I)

γ = 90.00 º Rint = 0.0442

3 V = 3150.2(8) Å  max = 27.50º

Z = 2 h = -15  15

-3 Dx = 1.279 Mg m k = -11  11

Mo K radiation l = -38 38

Cell parameters from 6801 reflections

 = 1.38±27.50º

 = 0.518 mm-1

T = 170 (2) K

Irregular, black

0.37 0.21 0.10 mm

338

Table AI-28c. Refinement Figure AI-28a. ORTEP plot of title compound.

Ellipsoids are at the 50% probability level. The

labels of H atoms are omitted for clarity.

Refinement on F2

R[F2 > 2(F2)] = R1 = 0.0416 wR(F2) = 0.1497

S = 0.672

7204 reflections

388 parameters

H-atom parameters constrained

2 2 2 w = 1/[ (Fo ) + (0.2000 P) + 0.0000P]

2 2 where P = (Fo + 2Fc )/3

(/)max = 0.141

-3 max = 0.478 eÅ

-3 min = -0.434 eÅ

Table AI-28d. Selected geometric parameters (Å, º). Fe1-O1 1.8856(15) O1-Fe- O2 98.71(6) Fe1-O2 2.0099(14) O1-Fe1-N1 170.29(7) Fe1-N1 2.0313(17) O2-Fe1-N1 86.89(6) Fe1-N2 2.0396(17) O1-Fe1-N2 88.75(7) Fe1-O2 2.0814(15) O2-Fe1-N2 169.02(6) Fe1-O3 2.2046(17) N1-Fe1-N2 86.89(7) O2-C6 1.349(2) O1-Fe1-O2 93.40(6) O2-Fe1 2.0814(15) O2-Fe1-O2 77.05(6) O1-C32 1.313(3) N1-Fe1-O2 95.60(6) C17-N3 1.320(3) N2-Fe1-O2 94.56(6) C17-N2 1.390(3) O1-Fe1-O3 86.39(7) C17-C18 1.449(3) O2-Fe1-O3 89.99(6) N3-C1 1.328(3) N1-Fe1-O3 85.67(7) N2-C20 1.358(3) N2-Fe1-O3 98.56(6) N1-C4 1.362(2) O2-Fe1-O3 166.87(6) N1-C1 1.385(3) C6-O2-Fe1 123.22(12) C3-C2 1.375(3) C6-O2-Fe1 119.67(12)

339

C3-C4 1.416(3) Fe1-O2-Fe1 102.95(6) C2-C1 1.448(3) C32-O1-Fe1 134.69(14) C2-C11 1.465(3) N3-C17-N2 127.17(18) C4-C5 1.458(3) N3-C17-C18 123.39(19) C21-C26 1.394(3) N2-C17-C18 109.43(18) C21-C22 1.397(3) C17-N3-C1 125.00(18) C21-C18 1.474(3) C20-N2-C17 107.01(17) C20-C19 1.430(3) C20-N2-Fe1 126.26(14) C20-C27 1.443(3) C17-N2-Fe1 126.47(14) C5-C10 1.404(3) C4-N1-C1 106.93(17) C5-C6 1.412(3) C4-N1-Fe1 125.74(14) C6-C7 1.403(3) C1-N1-Fe1 127.27(13) C32-C31 1.404(3) C2-C3-C4 108.36(19) C32-C27 1.423(3) C3-C2-C1 105.42(18) C19-C18 1.373(3) C3-C2-C11 127.02(19) C7-C8 1.376(3) C1-C2-C11 127.56(19) C27-C28 1.414(3) N3-C1-N1 126.54(19) C11-C12 1.395(3) N3-C1-C2 123.77(19) C11-C16 1.399(3) N1-C1-C2 109.39(18) C26-C25 1.378(3) N1-C4-C3 109.85(18) C31-C30 1.370(3) N1-C4-C5 123.57(18) C9-C10 1.379(3) C3-C4-C5 126.32(19) C9-C8 1.396(3) C26-C21-C22 117.6(2) C12-C13 1.385(3) C26-C21-C18 123.0(2) C13-C14 1.376(4) C22-C21-C18 119.4(2) C30-C29 1.385(4) N2-C20-C19 109.78(19) C22-C23 1.388(3) N2-C20-C27 124.28(19) C16-C15 1.381(4) C19-C20-C27 125.91(19) C14-C15 1.391(4) C10-C5-C6 118.32(19) C25-C24 1.382(4) C10-C50C4 118.99(19) C28-C29 1.381(4) C6-C5-C4 122.59(19) C23-C24 1.369(4) O2-C6-C7 118.66(18) O3-C33 1.452(3) O2-C6-C5 121.82(18) O3-C36 1.465(3) C7-C6-C5 119.53(19) C33-C34 1.516(4) O1-C32-C31 118.6(2) C36-C35 1.514(4) O1-C32-C27 122.70(19) C35-C34 1.510(4) C31-C32-C27 118.7(2) C18-C19-C20 108.19(19) C8-C7-C6 120.9(2) C28-C27-C32 117.6(2) C28-C27-C20 119.6(2) C32-C27-C20 122.79(19) C12-C11-C16 118.0(2) C12-C11-C2 122.5(2)

340

C16-C11-C2 119.4(2) C19-C18-C17 105.58(19) C19-C18-C21 126.7(2) C17-C18-C21 127.7(2) C25-C26-C21 121.3(2) C30-C3- C32 121.8(2) C10-C9-C8 119.9(2) C9-C10-C5 121.4(2) C13-C12-C11 120.6(2) C14-C13-C12 120.9(3) C31-C30-C29 120.4(2) C23-C22-C21 120.6(3) C7-C8-C9 119.9(2) C15-C16-C11 120.9(2) C13-C14-C15 119.1(2) C26-C25-C24 120.3(3) C29-C28-C27 122.2(2) C16-C15-C14 120.4(3) C24-C23-C22 120.8(2) C28-C29-C30 119.3(2) C33-O3-C36 108.12(19) C33-O3-Fe1 116.81(14) C36-O3-Fe1 131.51(15) O3-C33-C34 106.5(2) O3-C36-C35 104.0(2) C34-C3- C36 101.4(2) C35-C34-C33 102.3(2) C23-C24-C25 119.4(2)

341

Appendix II. NMR Spectra of Synthesized New Compounds

Figure AII-1. 1H NMR Spectrum of 2,6-di(Bpin)Naphthalene

342

Figure AII-2. 1H NMR Spectrum of 2,7-di(Bpin)Naphthalene

343

31 1 Figure AII-3. P{ H} NMR Spectrum of PCy3Au-2-Naphthyl

344

1 Figure AII-4. H NMR Spectrum of PCy3Au-2-Naphthyl

345

31 1 Figure AII-5. P{ H} NMR Spectrum of 2,6-bis(PCy3Au)naphthalene

346

1 Figure AII-6. H NMR Spectrum of 2,6-bis(PCy3Au)naphthalene

347

31 1 Figure AII-7. P{ H} NMR Spectrum of 2,7-bis(PCy3Au)naphthalene

348

1 Figure AII-8. H NMR Spectrum of 2,7-bis(PCy3Au)naphthalene

349

31 1 Figure AII-9. P{ H} NMR Spectrum of PPh3Au-2-naphthyl

350

1 Figure AII-10. H NMR Spectrum of PPh3Au-2-naphthyl

351

31 1 Figure AII-11. P{ H} NMR Spectrum of 2,6-bis(PPh3Au)naphthalene

352

31 Figure AII-12. H NMR Spectrum of 2,6-bis(PPh3Au)naphthalene

353

31 1 Figure AII-13. P{ H} NMR Spectrum of 2,7-bis(PPh3Au)naphthalene

354

1 Figure AII-14. H NMR Spectrum of 2,7-bis(PPh3Au)naphthalene

355

Figure AII-15. 1H NMR Spectrum of SIPrAu-2-naphthyl

356

Figure AII-16. 13C{1H} NMR Spectrum of SIPrAu-2-naphthyl

357

Figure AII-17. 1H NMR Spectrum of 2,6-bis(SIPrAu)naphthalene

358

Figure AII-18. 13C{1H} NMR Spectrum of 2,6-bis(SIPrAu)naphthalene

359

Figure AII-19. 1H NMR Spectrum of 2,7-bis(SIPrAu)naphthalene

360

Figure AII-20. 13C{1H} NMR Spectrum of 2,7-bis(SIPrAu)naphthalene

361

Figure AII-21. 1H NMR Spectrum of SIPrAu-tert-butylethynyl

362

Figure AII-22. 1H NMR Spectrum of SIPrAu-2-naphthylethynyl

363

Figure AII-23. 13C{1H} NMR Spectrum of SIPrAu-1-naphthylethynyl

364

Figure AII-24. 1H NMR Spectrum of SIPrAu-2-pyrenylethynyl

365

Figure AII-25. 13C{1H} NMR Spectrum of SIPrAu-1-pyrenylethynyl

366

Figure AII-26. 1H NMR Spectrum of SIPrAu-ferrocenylethynyl

367

Figure AII-27. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-(2-naphthyl)triazolato)

368

Figure AII-28. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-tert-butyltriazolato)

369

Figure AII-29. 1H NMR Spectrum of SIPrAu-(1-benzyl-4-ferrocenyltriazolato)

370

Figure AII-30. 31P{1H} NMR Spectrum of

PPh3Au-(1-benzyl-4-carboxylmethyltriazolato)

371

1 Figure AII-31. H NMR Spectrum of PPh3Au-(1-benzyl-4-carboxylmethyltriazolato)

372

31 1 Figure AII-32. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-phenyltriazolato)

373

1 Figure AII-33. H NMR Spectrum of PPh3Au-(1-benzyl-4-phenyltriazolato)

374

1 Figure AII-34. H NMR Spectrum of PPh3Au-(1-benzyl-4-(4-tolyl)triazolato)

375

1 Figure AII-35. H NMR Spectrum of PPh3Au-(1-benzyl-4-(4-tolyl)triazolato)

376

Figure AII-36. 31P{1H} NMR Spectrum of

PPh3Au-(1-benzyl-4-(4-fluorophenyl)triazolato)

377

Figure AII-37. 1H NMR Spectrum of

PPh3Au-(1-benzyl-4-(4-fluorophenyl)triazolato)

378

31 1 Figure AII-38. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-(3-thienyl)triazolato)

379

1 Figure AII-39. H NMR Spectrum of PPh3Au-(1-benzyl-4-(3-thienyl)triazolato)

380

31 1 Figure AII-40. P{ H} NMR Spectrum of PPh3Au-(1-benzyl-4-ferrocenyltriazolato)

381

1 Figure AII-41. H NMR Spectrum of PPh3Au-(1-benzyl-4-ferrocenyltriazolato)

382

Figure AII-42. 31P{1H} NMR Spectrum of

PCy3Au-(1-benzyl-4-(4-biphenyl)triazolato)

383

1 Figure AII-43. H NMR Spectrum of PCy3Au-(1-benzyl-4-(4-biphenyl)triazolato)

384

Figure AII-44. 31P{1H} NMR Spectrum of

PCy3Au-(1-benzyl-4-(1-naphthyl)triazolato)

385

1 Figure AII-45. H NMR Spectrum of PCy3Au-(1-benzyl-4-(1-naphthyl)triazolato)

386

Figure AII-46. 31P{1H} NMR Spectrum of

PCy3Au-(1-benzyl-4-(2-naphthyl)triazolato)

387

1 Figure AII-47. H NMR Spectrum of PCy3Au-(1-benzyl-4-(2-naphthyl)triazolato)

388

Figure AII-48. 31P{1H} NMR Spectrum of

PCy3Au-(1-benzyl-4-(9-phenanthryl)triazolato)

389

1 Figure AII-49. H NMR Spectrum of PCy3Au-(1-benzyl-4-(9-phenanthryl)triazolato)

390

Figure AII-50. 1H NMR spectrum of 1,4-dibromo-2,5-bis(4-tert-butylstyryl)benzene

391

Figure AII-51. 1H NMR spectrum of 1,4-dibromo-2,5-bis(4-bromostyryl)benzene

392

Figure AII-52. 1H NMR spectrum of 1-Bpin-4-(4-tert-butylstyryl)benzene

393

Figure AII-53. 1H NMR spectrum of 1,4-bis(Bpin)-2,5-bis(4-tert-butylstyryl)benzene

394

Figure AII-54. 1H NMR spectrum of 1,4-bis(4-Bpin-styryl)benzene

395

Figure AII-55. 1H NMR spectrum of 1,4-bis(Bpin)-2,5-bis(4-Bpin-styryl)benzene

396

Figure AII-56. 31P{1H} NMR spectrum of

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

397

1 Figure AII-57. H NMR spectrum of (E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

398

Figure AII-58. 31P{1H} NMR spectrum of

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

399

Figure AII-59. 1H NMR spectrum of

1,4-Bis[(PCy3)Au]-2,5-bis(4-tert-butylstyryl)benzene

400

Figure AII-60. 31P{1H} NMR spectrum of

2,5-bis(4-tert-butylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

401

Figure AII-61. 1H NMR spectrum of

2,5-bis(4-tert-butylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

402

Figure AII-62. 31P{1H} NMR spectrum of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

403

Figure AII-63. 1H NMR spectrum of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

404

31 1 Figure AII-64. P{ H} NMR spectrum of 1,4-bis(4-[(PCy3)Au]styryl)benzene

405

1 Figure AII-65. H NMR spectrum of 1,4-bis(4-[(PCy3)Au]styryl)benzene

406

Figure AII-66. 31P{1H} NMR spectrum of

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

407

Figure AII-67. 1H NMR spectrum of

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

408

Figure AII-68. 31P{1H} NMR spectrum of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

409

Figure AII-69. 1H NMR spectrum of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

410

Figure AII-70. 31P{1H} NMR spectrum of

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

411

Figure AII-71. 1H NMR spectrum of

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

412

31 1 Figure AII-72. P{ H} NMR spectrum of 2,6-bis(4-[(PCy3)Au]styryl)naphthalene

413

1 Figure AII-73. H NMR spectrum of 2,6-bis(4-[(PCy3)Au]styryl)naphthalene

414

Figure AII-74. 31P{1H} NMR spectrum of

2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene

415

1 Figure AII-75. H NMR spectrum of 2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene

416

Figure AII-76. 31P{1H} NMR spectrum of

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

417

Figure AII-77. 1H NMR spectrum of

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

418

Figure AII-78. 31P{1H} NMR spectrum of

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

419

Figure AII-79. 1H NMR spectrum of

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

420

Figure AII-80. 1H NMR spectrum of (0Z)-N-(3,5-bis(4-bromophenyl)-2H-pyrrol-2-ylidene)-3,5-bis(4-bromophenyl)-1H-p

yrrol-2-amine (Ld)

421

31 1 Figure AII-81. P{ H} NMR spectrum of PMe2PhAuLd

422

1 Figure AII-82. H NMR spectrum of PMe2PhAuLd

423

31 1 Figure AII-83. P{ H} NMR spectrum of PMe2PhAuLaBr2

424

1 Figure AII-84. H NMR spectrum of PMe2PhAuLaBr2

425

31 1 Figure AII-85. P{ H} NMR spectrum of PMe2PhAuLbBr2

426

1 Figure AII-86. H NMR spectrum of PMe2PhAuLbBr2

427

31 1 Figure AII-87. P{ H} NMR spectrum of PMe2PhAuLcBr2

428

1 Figure AII-88. H NMR spectrum of PMe2PhAuLcBr2

429

31 1 Figure AII-89. P{ H} NMR spectrum of PMe2PhAuLdBr2

430

1 Figure AII-90. H NMR spectrum of PMe2PhAuLdBr2

431

Appendix III Absorption and Emission Spectra for Selected

Compounds

2,6-dibromonaphthalene 6000 25

Solvent: CH Cl 270 nm 2 2 348 nm 520 nm C=1.12E-4 M 5000 280 nm Ex: 318 nm 20 494 nm

4000 Emission Intensity (a.u.) 290 nm 15 ) -1 3000 559 nm cm -1 10 (M

 2000

5 1000 668 nm 314 nm 697 nm 330 nm 0 0 250 300 350 400 450 500 550 600 650 700 750 800 850 wavelength (nm)

Figure AIII-1. Absorption and Emission Spectra of 2,6-dibromonaphthalene

2,7-dibromonaphthylene 7000 10 Solvent: CH Cl 2 2 6000 C=1.22E-4 M 274 nm Ex: 312 nm 8 5000 283 nm 490 nm IntensityEmission (a.u.) 520 nm

) 265 nm 6 -1 4000 390 nm cm -1

293 nm

(M 3000

 4

2000

656 nm 2 1000 312 nm 688 nm 327 nm

0 0 250 300 350 400 450 500 550 600 650 700 750 800 wavelength (nm)

Figure AIII-2. Absorption and Emission Spectra of 2,7-dibromonaphthalene

432

PPh Au-2-Naphthyl 3 10000 481 nm Solvent: THF 120 516 nm 353 nm C=2E-5M 8000 Ex: 275 nm 100 Emission Intensity (a.u.) Intensity Emission 6000 80 ) -1 555 nm 60 cm

-1 4000 M   40

2000 600 nm 20

0 0 300 400 500 600 700 800 wavelength (nm)

Figure AIII-3. Absorption and Emission Spectra of PPh3Au-2-naphthyl

2,6-(PPh Au) -naphthyl 3 2 100000 261 nm Solvent: CH Cl 300 490 nm 2 2 524 nm 80000 C=5.74 E-6 M 250 Ex: 307 nm (5.74E-5 M) Emission Intensity(a.u.)

60000 200 ) -1 cm 150 -1 40000 (M

 565 nm 308 nm 100

20000 614 nm 50

0 0 250 300 350 400 450 500 550 600 650 700 750 wavelength (nm)

Figure AIII-4. Absorption and Emission Spectra of 2,6-(PPh3Au)-naphthyl

433

2,7-(PPh3Au)2-naphthyl 80000 20

Solvent: CH2Cl2 70000 C=5.74 E-6 M 525 nm Ex: 310 nm (4.98 E-6 M) 490 nm 60000 15 Emission Intensity (a.u.) Intensity Emission

50000 ) -1 40000 10

cm 563 nm -1 (M

 30000

20000 5

10000

0 0 250 300 350 400 450 500 550 600 650 700 750 Wavelength (nm)

Figure AIII-5. Absorption and Emission Spectra of 2,7-(PPh3Au)-naphthyl

SIPr-Au-2-naphthyl 8000 25 Solvent: THF 480 nm C = 2 E-5 M Ex: 326 nm 20 6000 516 nm Emission Intensity(a.u.) 360 nm 15 )

-1 4000 cm

-1 371 nm 10 (M  556 nm 2000 5

326 nm 0 0 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-6. Absorption and Emission Spectra of SIPrAu-2-naphthyl

434

2,6-(SIPrAu)2-Naphthyl 50000 490 nm 400 solvent: CH Cl 2 2 524 nm C=8.45E-6 M 350 40000 Ex: 324 nm

300 Emission Intensity(a.u.)

30000 250 ) -1

cm 200 -1 20000 (M  564 nm 150 310 nm 100 10000

352 nm 611 nm 50

0 0 250 300 350 400 450 500 550 600 650 700 750 800 wavelength (nm)

Figure AIII-7. Absorption and Emission Spectra of 2,6-(SIPrAu)-naphthyl

2,7-(SIPrAu) -Naphthyl 2 60000 160 490 nm 526 nm Solvent: CH Cl 2 2 140 50000 C=8.45E-6 M 120

Ex: 313 nm Emission Intensity (a.u.) 40000 100 ) -1 30000 564 nm 80 cm -1

(M 60  20000

10000 609 nm 20 355 nm 370 nm

0 0 250 300 350 400 450 500 550 600 650 700 750 wavelength (nm)

Figure AIII-8. Absorption and Emission Spectra of 2,7-(SIPrAu)-naphthyl

435

PCy Au(9-phenanthrylethynyl) 3

3000 solvent: THF 331 nm C=2.65E-4M 200 385 nm Ex: 330 nm 2500 316 nm 366 nm

150 (a.u.) Intensity Emission 2000 ) -1 cm

-1 1500 406 nm 100 (M  529 nm 1000

577 nm 50 500

0 0 250 300 350 400 450 500 550 600 650 700 750 wavlength (nm)

Figure AIII-9. Absorption and Emission Spectra of PCy3Au(9-phenanthrylethynyl)

SIPrAu(1-pyrenylethynyl) 50000 10 Solvent: THF C=1.6E-5M Ex: 361 nm 383 nm 40000 650 nm 8 Emission Intensity (a.u.) Intensity Emission

30000 361 nm 6 ) -1 290 nm cm

-1 668 nm

20000 4 (Lmol  392 nm 708 nm 726 nm 10000 2

0 0 250 300 350 400 450 500 550 600 650 700 750 Wavelength (nm)

Figure AIII-10. Absorption and Emission Spectra of SIPrAu(1-pyrenylethynyl)

436

(PCy )Au(1-benzyl-4-(4-biphenyl)triazolato) 3 60 20000 Solvent: 2-MeTHF 305 nm 363 nm c=5.1E-5M 50 489 nm Ex: 325 nm

15000 522 nm

40 (a.u.) Intensity Emission ) -1 30 cm 10000 -1 (M  20

5000 10

0 0 250 300 350 400 450 500 550 600 650 700 750 wavelength (nm)

Figure AIII-11. Absorption and Emission Spectra of

PCy3Au(1-benzyl-4-(4-biphenyl)triazolato)

(PCy )Au(1-benzyl-4-(1-naphthyl)triazolato) 3

Solvent: 2-MeTHF 8000 309 nm 800 389 nm C= 3.94E-5 M Ex: 325 nm

6000 600 Emission Intensity (a.u.) Intensity Emission ) -1 cm

-1 4000 400 (M  530 nm

2000 200

0 0 250 300 350 400 450 500 550 600 650 700 750 Wavelength (nm)

Figure AIII-12. Absorption and Emission Spectra of

PCy3Au(1-benzyl-4-(1-naphthyl)triazolato)

437

[(PCy )Au(1-benzyl-4-(2-naphthyl)triazolato)] 3 0.35 Solvent: 2-MeTHF 16 Ex: 325 nm 0.30 532 nm 14 387 nm 567 nm 12 0.25 Emission Intensity (a.u.) Intensity Emission 10 )

-1 0.20 302 nm 8 cm -1 0.15 6 (M  4 0.10 2 0.05 0

0.00 -2 300 400 500 600 700 800 Wavelength (nm)

Figure AIII-13. Absorption and Emission Spectra of

PCy3Au(1-benzyl-4-(2-naphthyl)triazolato)

(PCy )Au(1-benzyl-4-(9-phenanthryl)triazolato) 3 16000 60 263 nm Solvent: 2-MeTHF 14000 c=6.16E-5 M 531 nm Ex: 325 nm 50 561 nm 12000

40 (a.u.) INtensity Emission 10000 311 nm 385 nm ) -1 8000 30 cm -1

(M 6000  20

4000

10 2000

0 0 250 300 350 400 450 500 550 600 650 700 750 wavelength (nm)

Figure AIII-14. Absorption and Emission Spectra of

PCy3Au(1-benzyl-4-(9-phenanthryl)triazolato)

438

1-Bpin-4-(4-tert-butylstyryl)benzene 50000

Solvent: CH Cl 250 324 nm 373 nm 2 2 C=1.66E-5 M 40000 Ex: 324 nm 200

30000 (a.u.) Intensity Emission 150 ) -1 cm

-1 20000 100 (M 

10000 50

0 0 250 300 350 400 450 500 Wavelength (nm)

Figure AIII-15. Absorption and Emission Spectra of 1-bpin-4-(4-tert-butylstyryl)benzene

1,4-bis(4-Bpin-styryl)benzene 120

368 nm 427 nm Solvent: CH Cl 50000 2 2 403 nm C=9.36E-6 M 100 Ex: 368 nm 40000

80 (a.u.) Intensity Emission )

-1 30000 454 nm 60 cm -1 (M

 20000 40

10000 20

0 0 250 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-16. Absorption and Emission Spectra of 1,4-bis(4-bpin-styryl)benzene

439

1,4-bis(Bpin)-2,5-bis(4-Bpin-styryl)benzene 400 40000 Solvent: CH Cl 373 nm 437 nm 2 2 414 nm 350 35000 C=6.23E-6M Ex: 373 nm 300 30000 Emission Intensity (a.u.) 250

) 25000 -1 463 nm

cm 200

-1 20000 (M

 150 15000

10000 100

5000 50

0 0 250 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-17. Absorption and Emission Spectra of 1,4-bis(bprin)-2,5-bis(4-bpin-styryl)benzne

(E)-1-[(PCy )Au]-4-(4-tert -butylstyryl)benzene 3

328 nm 160 60000 374 nm Solvent: 2-MeTHF 288 nm c=3.51E-6 M 140 Ex: 325 nm 50000 120 Emission Intensity(a.u.)

) 40000 345 nm -1 100 cm -1 30000 80 (M  60 20000 40

10000 20

0 0 250 300 350 400 450 500 Wavelength (nm)

Figure AIII-18. Absorption and Emission Spectra of

(E)-1-[(PCy3)Au]-4-(4-tert-butylstyryl)benzene

440

2,5-bis(4-tert-butylstyryl)-1,4-Bis ([(PCy )Au]ethynyl)benzene 3

427 nm Solvent: CH Cl 50000 2 2 324 nm 400 C=1.43E-5M Ex: 371 nm 40000 300 (a.u.) Intensity Emission ) -1 30000 cm

-1 371 nm 200 (M  20000

100 10000

0 0 250 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-19. Absorption and Emission Spectra of

2,5-bis(4-tert-butylstyryl)-1,4-bis([(PCy3)Au]ethynyl)benzene

2,5-bis(4-[(PCy )Au]ethynylstyryl)-1,4-Bis([(PCy )Au]ethynyl)benzene 3 3

333 nm 800 70000 468 nm Solvent: CH Cl 447 nm 2 2 C=1.31E-5 M 700 60000 Ex: 389 nm 600 50000 389 nm Emission Intensity (a.u.) Intensity Emission

) 500 -1 40000

cm 282 nm 400 -1 30000 (M  300

20000 200

10000 100

0 0 250 300 350 400 450 500 550 600 650 Wavelength (nm)

Figure AIII-20. Absorption and Emission Spectra of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-Bis([(PCy3)Au]ethynyl)benzene

441

1,4-bis(4-[(PCy )Au]styryl)benzene 3

14000 70 373 nm 411 nm solvent: CH Cl 2 2 C=1.62E-5M 12000 389 nm 60 Ex: 373 nm

10000 50 (a.u.) Intensity Emission )

-1 8000 40 cm -1 6000 30 (M 

4000 20

2000 10

0 0 250 300 350 400 450 500 550 600 650 wavelength (nm)

Figure AIII-21. Absorption and Emission Spectra of

1,4-bis(4-[(PCy3)Au]styryl)benzene

2,5-bis(4-[(PCy )Au]styryl)-1,4-dibromobenzene 3 500 375 nm 429 nm Solvent: CH Cl 25000 2 2 C=2.15E-5 M Ex: 375 nm 400 20000

455 nm (a.u.) Intensity Emission 403 nm 300

) 15000 -1 cm -1 M

 200

 10000

5000 100

0 0 250 300 350 400 450 500 550 600 650 Wavelength (nm)

Figure AIII-22. Absorption and Emission Spectra of

2,5-bis(4-[(PCy3)Au]styryl)-1,4-dibromobenzene

442

2,5-bis(4-[(PCy )Au]ethynylstyryl)-1,4-dibromobenzene 3

383 nm 600 448 nm Solvent: CH Cl 40000 2 2 C=1.67E-5 M 421 nm Ex: 383 nm 500 Emission Intensity(a.u.) 30000 400 ) -1 279 nm 300

cm 20000 -1 (M  200

10000 100

0 0 250 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-23. Absorption and Emission Spectra of

2,5-bis(4-[(PCy3)Au]ethynylstyryl)-1,4-dibromobenzene

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene 45000 800 Solvent: CH Cl 40000 2 2 C=6.55 E-6 M 700 35000 Ex: 378 nm 378 nm 462 nm 600 (a.u.) Intensity Emission 30000

) 255 nm 500

-1 25000

cm 400 -1 20000 260 nm (M  15000 300

10000 200

5000 100

0 0 250 300 350 400 450 500 550 600 650 700 Wavelength (nm)

Figure AIII-24. Absorption and Emission Spectra of

2,5-bis(4-[(PCy3)Au]triazolatostyryl)-1,4-dibromobenzene

443

2,6-bis(4-[(PCy )Au]styryl)naphthalene 3 600 60000 371 nm 412 nm Solvent: CH Cl 2 2 C= 3.11E-6M 500 50000 Ex: 371 nm

400 (a.u.) Intensity Emission 40000 ) -1 291 nm 300 cm

-1 30000 (M  200 20000

10000 100

0 0 250 300 350 400 450 500 550 600 Wavelength (nm)

Figure AIII-25. Absorption and Emission Spectra of

2,6-bis(4-[(PCy3)Au]styryl)naphthalene

2,6-bis(4-[(PCy )Au]ethynylstyryl)naphthalene 3 12000 350

248 nm 435 nm Solvent: CH Cl 2 2 300 10000 C=4.5E-5M 300 nm 383 nm Ex: 383 nm 250 8000 ) Emission Intensity (a.u.)

-1 200

cm 6000 -1 150 (M  4000 100

2000 50

0 0 200 250 300 350 400 450 500 550 600 650 wavelength (nm)

Figure AIII-26. Absorption and Emission Spectra of

2,6-bis(4-[(PCy3)Au]ethynylstyryl)naphthalene

444

2,6-bis(4-[(PCy )Au]styryl)-1,5-dibromonaphthalene 3 8000 600 454 nm 245 nm Solvent: CH Cl 7000 430 nm 2 2 C=6.93E-5 M 500

6000 Ex: 380 nm

400 5000 (a.u.) Intensity Emission ) -1 4000 300 cm -1 (M  3000 200

2000

100 1000

0 0 300 400 500 600 700 Wavelength (nm)

Figure AIII-27. Absorption and Emission Spectra of

2,6-bis(4-[(PCy3)Au]styryl)-1,5-dibromonaphthalene

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene 50000 80 389 nm 440 nm Solvent: CH Cl 2 2 70 C=2.01E-5 M 40000 Ex: 389 nm 60

415 nm (a.u.) Intensity Emission 315 nm 50

) 30000 -1

cm 40 -1

(M 20000  30

20 10000 10

0 0 250 300 350 400 450 500 550 600 650 700 wavelength (nm)

Figure AIII-28. Absorption and Emission Spectra of

2,6-bis(4-[(PCy3)Au]ethynylstyryl)-1,5-dibromonaphthalene

445

100000 20 L Br PMe PhAu 585 nm a 2 2 18 Solvent: 2-MeTHF 80000 C=1.74E-6 M 16 N Ex: 309 nm Br Br 14 Emission Intensity(a.u.) NN Au 60000 12 )

-1 Me P Me

cm 10 -1

(M 40000 8  309 nm 359 nm 6

20000 4

0 0 300 400 500 600 700 800 Wavelength (nm)

Figure AIII-29. Absorption and Emission Spectra of PMe2PhAuLaBr2

80000 40 610 nm L Br PMe PhAu b 2 2 Solvent: 2-MeTHF N C=1.96E-6 M 60000 Br Br 30 NN Ex: 315 nm Au

Me P Me (a.u.) Intensity Emission ) -1 40000 H3CO OCH3 20 cm -1 315 nm

(M 372 nm 

20000 10

400 nm

670 nm 0 0 300 400 500 600 700 800 Wavelength (nm)

Figure AIII-30. Absorption and Emission Spectra of PMe2PhAuLbBr2

446

60000 30 595 nm H3CO OCH3 L Br PMe PhAu c 2 2 50000 Solvent: 2-MeTHF

N C=2.96E-6 M

40000 Br Br Ex: 312 nm 20 (a.u.) Intensity Emission NN Au )

-1 Me P Me 30000 cm -1 (M  20000 10

372 nm 10000 312 nm

0 0 300 400 500 600 700 800 Wavelength (nm)

Figure AIII-31. Absorption and Emission Spectra of PMe2PhAuLcBr2

447

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