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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 By 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 i 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 ii 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 iv 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 v 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 vi 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.
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