BRNO UNIVERSITY OF TECHNOLOGY VYSOKÉ UČENÍ TECHNICKÉ V BRNĚ FACULTY OF CHEMISTRY FAKULTA CHEMICKÁ INSTITUTE OF CHEMISTRY AND TECHNOLOGY OF ENVIRONMENTAL PROTECTION ÚSTAV CHEMIE A TECHNOLOGIE OCHRANY ŽIVOTNÍHO PROSTŘEDÍ MODIFICATION OF ORGANIC HIGH PERFORMANCE PIGMENTS FOR APPLICATIONS IN ORGANIC ELECTRONICS MODIFIKACE ORGANICKÝCH VYSOCE VÝKONNÝCH PIGMENTŮ PRO APLIKACE V ORGANICKÉ ELEKTRONICE DOCTORAL THESIS DIZERTAČNÍ PRÁCE AUTHOR Ing. Martin Cigánek AUTOR PRÁCE SUPERVISOR doc. Ing. Jozef Krajčovič, Ph.D. ŠKOLITEL BRNO 2020 Specification Doctoral Thesis Institute of Chemistry and Technology of Department: Academic year: 2019/20 Environmental Protection Student: Ing. Martin Cigánek Study programme: Chemistry, Technology and Properties of Materials Study branch: Chemistry, Technology and Properties of Materials Head of thesis: doc. Ing. Jozef Krajčovič, Ph.D. Title of Doctoral Thesis: Modification of Organic High Performance Pigments for Applications in Organic Electronics Doctoral Thesis: 1 Write the review on organic high–performance pigments and related molecules and their application in the fields of organic electronics. 2 Write the review on synthetic possibilities of derivatization of appropriate organic pigments and related molecules. 3 Prepare and characterize a diverse range of novel original derivatives of organic pigments and related molecules with emphasis on the incorporation of adamantyl side chains into their structures. 4 Prepare and characterize a completely novel, as yet undescribed thiophene analogue of a benzodifuranone derivative (BDF). 5 Prepare and characterize an original fluorinated polymer based on thiophene with significantly prolonged π–conjugation of the monomer. 6 Perform a comprehensive study of the influence of adamantyl side chains on the resulting properties of the selected series of alkylated DPP derivatives. Deadline for Doctoral Thesis delivery: 18.8.2020: Ing. Martin Cigánek doc. Ing. Jozef Krajčovič, Ph.D. doc. Ing. Jiří Kučerík, Ph.D. Student Head of thesis Head of department prof. Ing. Martin Weiter, Ph.D. In Brno dated 1.9.2019 Dean Faculty of Chemistry, Brno University of Technology / Purkyňova 464/118 / 612 00 / Brno ABSTRACT The doctoral thesis deals with the study, synthesis and chemical derivatization of molecules belonging to the group of organic high-performance pigments and their potential application in the fields of organic electronics. The theoretical part of the work is focused on the latest trends in the area mentioned above, both from the application potential of specific derivatives and in terms of synthetic possibilities and their structural derivatization. The experimental part describes in detail the preparation of a wide range of intermediates and final products, including derivatives of diketopyrrolopyrroles (DPP), benzodifuranone (BDF), epindolidione (EP), naphthyridinedione (NTD) and thiophene-based polymer (PT). A total of 103 molecules were synthesized, of which 49 were final products, and 27 of them were completely novel, as yet unpublished. Herein, the main motive for the derivatization of pigment molecules is the incorporation of bulky adamantyl substituents into the resulting derivative structures. In the next part of the work, individual chemical modifications leading to the final products are discussed in more detail. In the series of N,N'-; N,O'- and O,O'-substituted DPP derivatives, the influence of both the alkyl chains’ character and binding position in the DPP molecule on the selectivity of the reaction, the thermal and optical properties of the resulting derivatives is comprehensively described. ABSTRAKT Dizertační práce pojednává o studiu, syntéze a chemické derivatizaci molekul spadajících do skupiny organických vysoce výkonných pigmentů a jejich potenciálním uplatnění v oblastech organické elektroniky. Teoretická část práce je zaměřena na nejnovější trendy v dané oblasti, a to jak z aplikačního potenciálu konkrétních derivátů, tak z pohledu syntetických možností a jejich strukturálních derivatizací. V experimentální části je pak podrobně popsána příprava pestré škály intermediátů a výsledných produktů, zahrnujících deriváty diketopyrrolopyrrolů (DPP), benzodifuranonu (BDF), epindolidionu (EP), naphthyridinedionu (NTD) a polymeru na bázi thiofenu (PT). Celkově bylo nasyntetizováno 103 molekul, přičemž 49 tvořily výsledné produkty, z nichž 27 bylo zcela nových, dosud nepublikovaných. Hlavním motivem derivatizace molekul pigmentů je zde inkorporace derivátů adamantanu do finálních struktur. V další části práce jsou blíže diskutovány jednotlivé chemické modifikace vedoucí k výsledným produktům. Na sérii N,N'-; N,O'- a O,O'-substituovaných derivátů DPP je popsána komplexní studie vlivu charakteru alkylových řetězců a také pozice jejich navázání v molekule DPP, a to nejen na selektivitu reakce, ale rovněž na optické i termické vlastnosti syntetizovaných produktů. 3 KEYWORDS Organic electronics, Pigment, Diketopyrrolopyrrole, Benzodifuranone, Epindolidione, Naphthyridinedione, Alkylation, Adamantane, Adamantyl, Asymmetric substitution KLÍČOVÁ SLOVA Organická elektronika, Pigment, Diketopyrrolopyrrol, Benzodifuranon, Epindolidion, Naphthyridinedion, Alkylace, Adamantan, Adamantyl, Asymetrická substituce 4 CIGÁNEK, Martin. Modification of Organic High Performance Pigments for Applications in Organic Electronics. Brno, 2020. Dostupné také z: https://www.vutbr.cz/studenti/zav- prace/detail/129357. Doctoral Thesis. Vysoké učení technické v Brně, Fakulta chemická, Institute of Chemistry and Technology of Environmental Protection. Supervisor Jozef Krajčovič. DECLARATION I declare that the doctoral thesis has been worked out by myself and that all the quotations from the used literary sources are accurate and complete. The content of the doctoral thesis is the property of the Faculty of Chemistry of Brno University of Technology and all commercial uses are allowed only if approved by both the supervisor and the dean of the Faculty of Chemistry, BUT. PROHLÁŠENÍ Prohlašuji, že jsem dizertační práci vypracoval samostatně a že všechny použité literární zdroje jsem správně a úplně citoval. Dizertační práce je z hlediska obsahu majetkem Fakulty chemické VUT v Brně a může být využita ke komerčním účelům jen se souhlasem vedoucího práce a děkana FCH VUT. ................................................. Ing. Martin Cigánek Acknowledgement: I want to thank my supervisor doc. Ing. Jozef Krajčovič, Ph.D for valuable advice, factual comments and helpfulness in consulting not only this work but during the entire doctoral study. I would also like to thank all my colleagues from the Faculty of Chemistry, Brno University of Technology for the characterization of the prepared substances and the creation of a creative and friendly working environment. I also thank the Faculty of Chemistry, Brno University of Technology for creating great and modern working conditions. In conclusion, I want to thank my family and my dear Hanka, without whose support the realization of this work would not be possible. 5 CONTENTS 1 OBJECTIVES OF THE DOCTORAL THESIS ............................................................ 11 2 INTRODUCTION ............................................................................................................. 12 3 THEORETICAL PART & REVIEW ............................................................................. 15 3.1 Organic electronics and photonics ................................................................................ 15 3.2 Organic materials for electronics .................................................................................. 15 3.2.1 Organic high-performance pigments ................................................................. 17 3.2.1.1 Diketopyrrolopyrroles (DPPs) ............................................................. 18 3.2.1.2 Benzodifuranones (BDFs) ..................................................................... 22 3.2.1.3 Derivatives of indigo (ID) and isoindigo (IID) ..................................... 24 3.2.2 Other structurally related substances ................................................................. 25 3.2.2.1 Derivatives of naphthyridinedione (NTD) ............................................ 25 3.2.2.2 Derivatives of polythiophene (PT) ........................................................ 27 4 TARGET MOLECULES AND THEIR SYNTHESIS ................................................... 31 4.1 Modification of DPP derivatives .................................................................................. 31 4.1.1 N,N'-alkylation ................................................................................................... 31 4.1.2 Variation of aromatic side chains ....................................................................... 33 4.1.2.1 Cross-coupling reactions ...................................................................... 34 4.1.2.2 Direct arylation ..................................................................................... 35 4.1.3 Incorporation of functional groups .................................................................... 36 4.1.3.1 Electron-donating groups ..................................................................... 37 4.1.3.2 Electron-accepting groups .................................................................... 37 4.1.4 Quinoid structures of DPPs ................................................................................ 39 4.1.5 Thioketo analogues of DPPs .............................................................................