Accessing Synthetically-Challenging Isoindole-Based Materials for Assessment in Organic Photovoltaics via Chemical and Engineering Methodologies by Jeremy Dang A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Department of Chemical Engineering and Applied Chemistry University of Toronto © Copyright by Jeremy Dang 2016 Accessing Synthetically-Challenging Isoindole-Based Materials for Assessment in Organic Photovoltaics via Chemical and Engineering Methodologies Jeremy Dang Doctor of Philosophy Department of Chemical Engineering and Applied Chemistry University of Toronto 2016 Abstract Isoindoles are a broad class of compounds that comprise a very small space within the domain of established photoactive materials for organic photovoltaics (OPVs). Given this scarcity, combined with the performance appeal of presently and well known isoindole-based compounds such as the phthalocyanines, it is a worthy undertaking to develop new materials in this domain. This thesis aims to bring to light the suitability of five novel, or underexplored, classes of isoindole-based materials for OPVs. These classes are the boron subphthalocyanine (BsubPc) polymers, oxygen-bridged dimers of BsubPcs (μ-oxo-(BsubPc) 2), boron subnaphthalocyanines (BsubNcs), group XIII metal complexes of 1,3-bis(2-pyridylimino)isodinoline (BPI), and the boron tribenzosubporphyrins (BsubPys). The synthesis of these materials was proven to be challenging as evident in their low isolated yields, lengthy synthetic and purification processes, and/or batch-to-batch variations. This outcome was not surprising given their undeveloped chemical nature. The photo- and electro- physical properties were characterized and shown to be desirable for all classes other than the ii group XIII metal complexes of BPI for OPVs. μ-Oxo-(BsubPc) 2 and BsubNcs show promise in this application while BsubPc polymers and BsubPys will be subjects of future exploration. The results from the work herein aid to develop and strengthen the fundamental understanding of the structure-property relationships of isoindole derivatives. On a broader scale, the work demonstrates their versatility as functional materials for OPVs and their possible expansion to other organic electronic technologies like organic light emitting diodes and organic field effect transistors. iii Acknowledgments I would like to begin by expressing my deepest gratitude to my supervisor, Professor Timothy P. Bender, for his support and guidance throughout my entire degree. You have taught me valuable lessons, given me the freedom to explore my research interests, and most importantly, broadened my perspective on the real-world applications of science. I will always appreciate your mentorship and your encouragement in having a well-balanced lifestyle. Thank you for the opportunity. I would also like to thank my committee members, Professor Dwight S. Seferos and Professor Christopher M. Yip, for their guidance in my Ph.D. journey. It has been a long and difficult one, but truly a humbling and worthwhile experience. Thank you for your insights and feedback in this process. To the Benderites/Weekday Benders/Bender Minions/Bending Bad Crew/Average Benders, thank you for a wonderful time. I will always remember and cherish the good moments… and even the bad ones. I'd like to specifically give thanks to Dr. Benoit Lessard, Anjuli Szawiola, Hasan Raboui, Katie Sampson, David Josey, Trevor Plint, Dr. Brett Kamino, Dr. John Grande, Dr. Jessica Virdo, Dr. Jeffrey Castrucci, Dr. Graham Morse, Dr. Andrew Paton, Dr. Catherine Bonnier, Mabel Fulford, Mike Gretton, Jane Cho, Ahmed Balawi, Mona Khatibi, Alex Peltekoff, Alaa Sifate, Stephanie Nyikos, Cynthia Cheung, Devon Holst, Richard Garner, Esmeralda Bukuroshi, and Aleksa Dovijarski. A departing message to all present and future Benderites, this is a great group filled with great people. Keep our unique dynamic identity strong within the group, as well as within the department. To my parents and brothers, I appreciate your efforts in trying to comprehend my research work. I am aware that this was not a simple task. I'd like to thank you for the endless support. Lastly, I'd like to thank my dear Anna. While I'm able to convey my scientific findings in this dissertation, I find that my words cannot do the same in expressing my admiration and appreciation for you. You exemplify the image of a hard-working, driven person and you have constantly aspired me to strive for more. I admittedly don't say it enough, but I love you very much and I look forward to the next chapter of our lives. iv Table of Contents List of Tables viii List of Figures ix List of Schemes xiii List of Abbreviations xiv Chapter 1: Introduction 1 1.1 The Solar Energy Paradigm 1 1.2 Brief History and Key Discoveries 2 1.3 Organic Photovoltaics (OPVs) - The Future of PV Technologies? 3 1.4 Operating Principles of OPVs 4 1.5 Device Architectures 6 1.6 Methods of Fabrication 8 1.7 Device Performance Definition 9 1.8 Optoelectronic Effects on Performance 11 1.9 Commonly Employed Organic Photoactive Materials 14 1.10 Isoindole-Based Compounds in OPVs 17 1.11 Thesis Statement 25 1.12 References 28 Chapter 2: A boron subphthalocyanine polymer: poly(4-methylstyrene)-co -poly(phenoxy-boron-subphthalocyanine) 36 2.1 Abstract 37 2.2 Introduction 37 2.3 Results and Discussion 38 2.4 Conclusions 51 2.5 References 52 v Chapter 3: Process for the synthesis of symmetric and unsymmetric oxygen bridged dimers of boron subphthalocyanines (μ-oxo(BsubPcs) 2s) 55 3.1 Abstract 56 3.2 Introduction 56 3.3 Results and Discussion 59 3.4 Conclusions 76 3.5 References 77 Chapter 4: Growth of μ-oxo-boron subphthalocyanine (μ-oxo(BsubPcs) 2) thin films via organic chemical vapor deposition (OCVD) 79 4.1 Abstract 80 4.2 Introduction 80 4.3 Results and Discussion 83 4.4 Conclusions 90 4.5 References 91 Chapter 5: The mixed alloyed chemical composition of chloro-(chloro) n-boron subnaphthalocyanines dictate their physical properties and performance in organic photovoltaic devices 94 5.1 Abstract 95 5.2 Introduction 95 5.3 Results and Discussion 100 5.4 Conclusions 119 5.5 References 121 Chapter 6: Phenoxy boron subnaphthalocyanines: synthesis, properties, and their applications in organic planar heterojunction photovoltaics 125 6.1 Abstract 126 6.2 Introduction 126 6.3 Results and Discussion 129 6.4 Conclusions 137 6.5 References 138 vi Chapter 7: Boron, aluminum, gallium, and indium complexes of 1,3-bis(2-pyridylimino)isoindoline (BPI) 141 7.1 Abstract 142 7.2 Introduction 142 7.3 Results and Discussion 144 7.4 Conclusions 151 7.5 References 153 Chapter 8: A synthetic and engineering process to boron tribenzosubporphyrins 155 8.1 Abstract 156 8.2 Introduction 156 8.3 Results and Discussion 159 8.4 Conclusions 176 8.5 References 177 Chapter 9: Summary and Future Work 179 9.1 Summary 179 9.2 Future Work 185 9.3 References 199 Appendix: General Experimental Section 203 Appendix A: Supplementary Information for Chapter 2 226 Appendix B: Supplementary Information for Chapter 3 206 Appendix C: Supplementary Information for Chapter 4 249 Appendix D: Supplementary Information for Chapter 5 254 Appendix E: Supplementary Information for Chapter 6 298 Appendix F: Supplementary Information for Chapter 7 335 Appendix G: Supplementary Information for Chapter 8 349 vii List of Tables Table 1.1. Number of publications for each of the listed organic photoactive material. 15 Table 1.2. Summary of reported BsubNc synthesis. 23 Table 3.1. Photophysical and electronic properties of µ-oxo-(BsubPc) 2, F12 BsubPc-O-BsubPc, Cl 6BsubPc-O-BsubPc, and Cl 12 BsubPc-O-BsubPc. 68 Table 3.2. Average device parameters of PHJ OPVs of the following configuration: ITO/PEDOT:PSS/α-6T/acceptor/TPBi/Ag or ITO/PEDOT:PSS/MoO x/donor/C 60/70 /TPBi/Ag. 75 Table 5.1. Photophysical properties of Cl-Cl nBsubNcs. 112 Table 5.2. Electrochemical properties of Cl-Cl nBsubNcs. 113 Table 5.3. Electrochemical properties (DPV) and ultraviolet photoelectron spectroscopy (UPS) characteristics of Cl-Cl nBsubNcs. 114 Table 5.4. Average device parameters of PHJ OPVs of the following configuration: ITO/PEDOT:PSS/α-6T(55 nm)/Cl-Cl nBsubNc(25 nm)/BCP(10 nm)/Ag(80 nm) whereby the Cl-Cl nBsubNc layer is made of nitrobenzene-Cl-Cl nBsubNc, p-cymene-Cl-Cl nBsubNc, literature-Cl-Cl nBsubNc, or commercial-Cl-Cl nBsubNc. 118 Table 6.1. X-ray diffraction results. 132 Table 6.2. Photophysical and electronic properties of phenoxy Cl nBsubNcs. 133 Table 6.3. Average device parameters of PHJ OPVs of the following configuration: ITO/PEDOT:PSS/α-6T(55 nm)/BsubNc(25 nm)/BCP(10 nm)/Ag(80 nm) whereby the BsubNc layer is either PhO-Cl nBsubNc or F 5-Cl nBsubNc. 136 Table 8.1. Device parameters of PHJ OPVs of the following configuration: ITO/PEDOT:PSS/MeO-n-BsubPy/Cl-Cl 12 BsubPc/BCP/Ag. 170 Table 9.1. Electronic properties of μ-oxo-(BsubPc) 2 and the unsymmetric variants. 187 Table 9.2. Device performance characteristics reported by Torres et al . and Jones et al . 188 Table 9.3. Attempted syntheses of Br-BsubNc. 195 Table 9.4. Attempted syntheses of F-BsubNc. 196 viii List of Figures Figure 1.1. Global energy consumption (in TW) per year since 1986. 1 Figure 1.2. Operating mechanism for Schottky cells. 6 Figure 1.3. Operating mechanism for donor-acceptor (D-A) heterojunction OPV cells. 6 Figure 1.4. Left to right : Device architecture of a Schottky cell, planar heterojunction (PHJ), bulk heterojunction (BHJ), and a tandem cell. 7 Figure 1.5. An example of a (a) vacuum deposition and (b) solution processing process. 9 Figure 1.6. A typical current density vs. voltage (J-V) curve of an OPV cell under illumination.