Synthesis and functionalisation of novel donor systems towards organic electronics

In our laboratory for organic synthesis in Leuven, a lot of synthetic methods have been developed concerning organic polycyclic donor systems such as pentacene, carbazoles and more recently indolo[3,2-b]carbazoles (ICZs). This project is related to the ICZs and will focus on developing new synthetic methodologies to prepare novel building blocks, which will be coupled with known acceptor moieties like diketopyrrolopyrrole (DPP), BODIPY and maleimides, to synthesize donor-acceptor materials which can be tested for organic electronics. The aim of this project is to provide a synthetic contribution to this research area. In first instance, the already available 2,8-functionalized ICZs will be converted to acceptor-donor-acceptor (A-D-A) molecules by coupling with complementary functionalized acceptor units. For this purpose, palladium catalyzed reactions such as Suzuki-, Stille- or Sonogashira coupling reactions will be used. Previous research showed that optimalization of the reaction conditions is of importance to obtain high yields for these reactions. The properties of these A-D-A molecules will be investigated by UV-VIS spectroscopy. The aim is to obtain a broad and intense absorbance over the visible wavelength range.Acknowledgements Samenvatting Summary List of abbreviations Table of contents Introduction 0.1 General introduction 0.2 Organic light emitting diode (OLED) 0.3 Organic field effect transistor (OFET) 0.4 Organic photovoltaic cell (OPV) 0.5 Synthesis of indolo[3,2-b]carbazoles 0.5.1 Oxidative and transition metal catalyzed synthesis 0.5.2 Synthesis starting from indoles 0.5.3 Fischer indole synthesis 0.5.4 Cadogan Synthesis 0.6 Functionalization of indolo[3,2-b]carbazole 0.7 Synthesis of pyrrolo[2,3-f]indole 0.8 Synthesis of furo[3,2-c]carbazole 0.9 Aim Chapter 1. Synthesis and functionalization of pyrrolo[2,3-f]indoles 1.1 Introduction 1.2 Synthesis of pyrrolo[2,3-f]indole 1.3 Modifications of non-alkylated pyrrolo[2,3-f]indole 1.4 Alkylation of pyrrolo[2,3-f]indole 1.5 Bromination of pyrrolo[2,3-f]indole 1.6 Palladium catalyzed coupling reactions 1.6.1 Suzuki cross coupling 1.6.2 Sonogashira coupling 1.6.3 Heck reaction 1.6.4 CH arylation of BODIPY 1.7 Formylation of pyrrolo[2,3-f]indole 1.8 Decarboxylation of alkylated pyrrolo[2,3-f]indole 1.9 Modfications to the alpha-position 1.10 Spectroscopic data 1.11 Conclusion 1.12 Experimental data Chapter 2. Synthesis and functionalization of benzodicarbazole 2.1 Literature synthesis of indolo[3,2-a]carbazole 2.2 Reproducing the reaction conditions with carbazole 2.3 Proposed reaction mechanism 2.4 Modifying the reaction conditions 2.5 Functionalization of the benzodicarbazole scaffold 2.5.1 Bromination of the benzodicarbazole scaffold 2.5.2 Acylation of the benzodicarbazole scaffold 2.5.3 Formylation of the benzodicarbazole scaffold 2.6 Exploration of functionalized benzil moieties 2.6.1 Synthesis with 9,10-phenanthrenequinone 2.6.2 Synthesis with 4,4’-dimethoxybenzil 2.6.3 Synthesis with 4,4’-dibromobenzil 2.6.4 Synthesis with 2,3-butanedione 2.7 Spectroscopic data 2.8 Conclusion 2.9 Experimental data Chapter 3. Synthesis and functionalization of furo[3,2-c]carbazoles 3.1 Synthesis of furo[3,2-c]carbazole 3.2 Synthesis of functionalized furo[3,2-c]carbazole 3.2.1 Functionalized benzil moieties 3.2.2 Proposed reaction mechanism for the intramolecular ring closure 3.2.3 Bromination of furo[3,2-c]carbazole 3.2.4 Coupling of furo[3,2-c]carbazole with BODIPY 3.2.5 Formylation of furo[3,2-c]carbazole 3.2.6 Condensation reactions of the aldehyde group 3.2.7 Horner-Wadsworth-Emmons reaction (HWE) 3.2.8 Synthesis of terminal alkyne 3.2.9 Nitration of furo[3,2-c]carbazole 3.3 Ring opening of the furan ring 3.4 Spectroscopic properties 3.5 Conclusion 3.6 Experimental data General conclusion and outlook Safety and environmental considerations Materials and methods List of publications List of attended conferences and symposianrpages: 210status: publishe