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Design, Synthesis and Properties of Pyrene-Fused Azaacenes and Their Applications in Organic Electronics

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Design, Synthesis and Properties of Pyrene-Fused Azaacenes and Their Applications in Organic Electronics Design, Synthesis and Properties of Pyrene-Fused Azaacenes and Their Applications in Organic Electronics INAUGURALDISSERTATION zur Erlangung des Doktorgrades der Fakultät für Chemie, Pharmazie und Geowissenschaften der Freiburg Institute of Advanced Studies, Soft Matter Research der Albert-Ludwigs-Universität Freiburg im Breisgau Vorgelegt von Sandeep Pandharinathrao More aus Jamb Nanded (India) 2013 - 1 - - 2 - Vorsitzender des Promotionsausschusses: Prof. Dr. Thorsten Koslowski Referent: Prof. Dr. Dietmar Plattner Korreferent: Prof. Dr. A. Mateo-Alonso Datum der Promotion: 21.10.2013 - 3 - - 4 - Teile dieser Dissertation wurden Veröffenlich: Publikationen: 1. "Versatile 2,7-substituted pyrene synthons for the synthesis of pyrene-fused azaacenes", Sandeep More, Rajesh Bhosale, Sunil Choudhray, Aurelio Mateo- Alonso, Org. Lett., 2012, 14, 4170-73. 2. “A tetraalkylated pyrene building block for the synthesis of pyrene fused azaacenes with enhanced solubility”, Niksa Kulisic, Sandeep More, Aurelio Mateo-Alonso, Chem. Comm. 2011, 47, 514-517. - 5 - - 6 - To my teachers - 7 - - 8 - Acknowledgements This thesis has been conducted in the Department of Organic Chemistry, Albert- Luwigs University, Freiburg under the direction of Prof. Aurelio Mateo-Alonso. I wish to express my sincere gratitude for giving me the opportunity to get into research in his group. During my work I enjoyed the untiring discussion with my supervisor. Much helpful advice and the moral support from Prof. Mateo-Alonso lead to success of my dissertation work in time. My gratitude also goes to Prof. Dr. Dietmar Plattner, who agreed to read my thesis and participated in as a referee. I also wish to convey my thanks to Dr. Keller, Mr. Reinbold and Ms. Schonhard from NMR department. Thanks also to Mr. Warth and Mr. Wörth for the MS, Dr. Thomann for TEM images and finally to Mr. Bär for the computer service. Special thanks to our collaborators, Prof. Ingo Krossing (Albert-Luwigs University, Freiburg) for the crystal structures and Prof. Emilio Palomares (ICIQ, Spain), Prof. Franco Cacialli (UCL, United Kingdom) and Prof. Dago De Leeuv (University of Groningen, The Netherlands) for the device studies of my molecules. Completion of this thesis would not have been possible without the wonderful skills and valuable advices of Dr. Niksa Kulisic and Dr. Rajesh Bhosale. I would also like to thank my colleagues Francesco Scarel, Sunil Choudhary, David Boschert, Sudhakar Gaikwad, Cinzia Spinato, Burkhardt Possel, Mads Grueninger for maintaining a congenial, fun filled atmosphere in the lab. Life in Freiburg would never been as great without Gaurima, Sachin, Sarika, Deblina, Vignesh, Rajeevan, Bobby, Pradipta and Bachhi who have been like a family to me. My deep gratitude goes to my teachers Dr. R. P. Pawar, Dr. W. N. Jadhav, Dr. H. B. Borate, Mr. V. N. Sonnekar, Mr. C. V. Magar, Mr. T. N. Dalave, Mr. B. P. Shinde, Mr. S. T. Chavan and Mr. Narwade without whom I could never be here. I would like to thank all my friends in Parbhani and Pune for their continuous encouragement and support. Finally, I extend enormous thanks to my father Dr. Pandharinathrao, my mother Late Mrs. Mitravrinda, my brother Mr. Sudarshanrao, my sister-in-law Mrs. Pratibha and my sister Dr. Archanadevi for their support, love and care. Last but not the least, with a warm heart, I would like to thank my nephews and nieces Somnath, Shambhavi, Shivani and Malhar for keeping me cheerful throughout the PhD. - 9 - - 10 - Contents 1. Small molecules for organic electronics 19 1.1 Introduction 21 1.1.1 Organic field effect transistors (OFETs) 21 1.1.1.1 Working principle 23 1.1.1.2 Use of organic molecules in OFETs 26 A. Use of conjugated polymers in OFETs 26 B. Use of small molecules in OFETs 27 1.1.2 Organic light emitting diodes (OLEDs) 36 1.1.2.1. Material used in OLEDs 38 A) Use of conjugated polymers in OLEDs 38 B) Use of small molecules in OLEDs 38 Use of acenes in OLEDs 39 Use of N containing PAHs in OLEDs 40 1.1.3 Organic photovoltaics (OPVs) 40 1.1.3.1 Use of organic material in OPVs 41 A) Use of conjugated polymers in OPVs 41 B) Use of small molecules in OPVs 42 Use of acenes in OPVs 43 Use of other PAHs in OPVs 44 1.2 References 47 2. Design, synthesis and properties of pyrene fused azaacenes 53 2.1 Introduction 55 2.1.1 Bandgap 56 2.1.2 Stability of acenes 57 2.1.3 Synthesis of acenes with greater stability 58 2.2 Heteroacenes 61 2.2.1 Introduction 61 2.2.2 Smaller azaacenes and oligo-azaacenes 61 2.2.3 Pyrene fused azaacenes 64 2.3 Synthesis of pyrene fused oligoacenes 70 2.3.1 Objective 70 2.3.2 Synthesis of non-substituted pyrene fused oligoacenes 71 2.3.2.1 Attempts to synthesize 5,6-dihydro-3b,7a-(epoxyethanooxy) [1,4] dioxino[ 2',3':9,10] phenanthro [4,5-abc]phenazine-13,14-diamine 71 Ist strategy 71 IInd strategy 72 2.3.2.2 Stepwise cyclocondensation from pyrene diketone or tetraketone 74 Ist strategy 74 IInd strategy 75 2.3.3 Attempts to synthesize di-tert.-butyl pyrene fused oligoazaacenes 75 - 11 - 2.3.3.1 Synthesis of 2,7-di-tert-butylphenanthro[4,5-abc]phenazine-11,12- diamine and further cyclocondensation 75 2.3.3.2 Attempt to synthesize 2,7-di-tert-butylpyrene fused octaazadodecacene 77 2.3.3.3 Synthesis of 5,6-dihydro-3b,7a-(epoxyethanooxy) [1,4]dioxino[2',3':9,10] 2,7-di-tert-butylphenanthro [4,5-abc]phenazine-13,14-diamine 78 Ist strategy 78 IInd strategy 79 IIIrd strategy 80 2.3.3.4 Attempts to synthesis of 2,7-di-tert-butylpyrene-4,5-diketals fused octaazadodecacene 82 2.6 Conclusion 84 2.7 References 85 3. Design, synthesis and properties of versatile 2,7-substituted pyrene fused azaacenes as low LUMO materials for OPVs 89 3.1 Introduction 91 3.1.1 1-Substituted pyrene 91 3.1.2 1,3,6,8-Substituted pyrene 92 3.1.3 4,5,9,10-Substituted pyrene 94 3.1.4 2,7-Substituted pyrene 95 3.2 Synthesis of 2,7-substituted pyrene-fused azaacenes 98 3.2.1 Objectives 98 3.2.2 Synthesis of 2,7-substituted pyrene tetraketone 99 3.2.3 Utilization of 2,7-substituted pyrene tetraketones for azaacene synthesis 100 3.2.4 Optical properties 101 3.2.5 Electrochemical properties 102 3.3 Low LUMO azaacene material synthesis 104 3.3.1 Optical properties of low LUMO azaacenes 105 3.3.2 Electrochemical properties of low LUMO materials 106 3.3.3 Photocurrent-Voltage Curves (J-V Profile) of 247 108 3.4 References 109 4. Synthesis and properties of “twisted” pyrene fused azaacenes 111 4.1 Introduction 113 4.2 Synthesis of Twistazaacene using bulky substituents 117 4.2.1 Objectives 117 4.2.2 Attempts to synthesize trimethylsillyl acetylene (TMS) substituted tetraazahexacene 117 Ist attempt 117 IInd attempt 118 4.2.3 Synthesis and crystal structure study of tri-isopropylsilyl (TIPS) acetylene substituted tetraazahexacene 119 - 12 - 4.2.4 Synthesis and crystal structure study of tri-isobutylsilyl (TIBS) acetylene substituted tetraazahexacene 121 4.2.5 Synthesis and crystal structure study of tri-phenylsilyl (TPS) acetylene substituted tetraazahexacene 123 4.3 Optical properties 125 4.4 Conclusion 126 4.5 References 127 5. Self-assembling properties of 2,7-substituted pyrene fused azaacenes 129 5.1 Introduction 131 5.2 Supramolecular self-assemblies of 2,7-substituted pyrene azaacenes 133 5.2.1 Self assemblies of compound 241a 134 5.2.2 Self assemblies of compound 241b 138 5.3 Conclusion 139 5.4 References 140 Experimental Procedures 143 Appendix 181 - 13 - - 14 - Abbreviations AcOH Acetic Acid °C Centigrade degree C-C Carbon-carbon C-N Carbon-nitrogen CHCl3 Chloroform d Doublet DCM Dichloromethane DFT Density Functional Theory DIPA di-iPropyl Amine DIPEA di-iPropylethyl Amine DMF Dimethylformamide EA Ethyl Acetate EI Electronic Impact eq Equivalent ESI Electrospray Ionization Et Ethyl EtOH Ethanol hrs Hours HCL Hydrochloric Acid HOMO Highest Occupied Molecular Orbital Hz Hertz i-Pr iso-Propyl J Coupling constant LUMO Lowest Unoccupoed Molecular Orbital m Multiplet Me Methyl mmol Milimolar MS Mass spectrommetry NMR Nuclear magnetic resonance NIR Near infrared ODCB o-Dichlorobenzene OFET Organic Field Effect Transistor OLED Organic Light Emitting Diode - 15 - OPV Organic Photovoltaic PE Petrolium Ether (40-60oC) Ph Phenyl PAH Polycyclic Aromatic Hydrocarbon ppm Parts per million PTSA p-Toluenesulphonic Acid PTSCl p-Toluenesulphonyl Chlorid rt Room temperature s Singlet T Temperature t Triplet TFA Trifluoroacetic acid THF Tetrahydrofuran TIBS tri-iButylsilyl TIPS tri-iPropylsilyl TLC Thin layer chromatography TMS Trimethylsilyl TPS Triphenylsilyl UV-Vis Ultraviolet-visible V Volts - 16 - - 17 - - 18 - Chapter: 1 Small Molecules for Organic Electronics - 19 - - 20 - 1.1. Introduction: The use of organic materials in electronic devices is motivated by their ease in tuning electronic and processing properties by chemical design and synthesis, relatively low cost processing, mechanical flexibility, and compatibility with flexible substrates. Among these electronic products, organic light-emitting diode (OLED) technology is already used in commercial applications such as displays for mobile phones and portable digital media players, car radios and digital cameras, while other technologies with great potential are under development such as organic field-effect transistors (OFET) and photovoltaic (OPV) solar cells. Nevertheless some device OFET and OPV prototypes are on the edge for market entry. Organic materials are also proving their economic and ecological benefits along with design and application options such as in large-area lighting, flexible displays, etc.1 Different types of organic material have been used in electronics in the form of conjugated polymers and small molecules.
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