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Synthesis of Annulated Π-Systems Based on a Tribenzotriquinacene Core

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Synthesis of Annulated Π-Systems Based on a Tribenzotriquinacene Core Synthesis of annulated -systems based on a tribenzotriquinacene core Dissertation zur Erlangung des naturwissenschaftlichen Doktorgrades der Julius-Maximilians-Universität Würzburg vorgelegt von Rachel Abigail Buschmann aus Derby, Großbritannien Würzburg 2019 Eingereicht bei der Fakultät für Chemie und Pharmazie am __________________________ Gutachter der schriftlichen Arbeit 1. Gutachter: __________________________________ 2. Gutachter: __________________________________ Prüfer des öffentlichen Promotionskolloquiums 1. Prüfer: __________________________________ 2. Prüfer: __________________________________ 3. Prüfer: __________________________________ Datum des öffentlichen Promotionskolloquiums __________________________ Doktorurkunde ausgehändigt am __________________________ For my family Don’t let anyone rob you of your imagination, your creativity or your curiosity. Mae Jemison Die vorliegende Arbeit wurde im Zeitraum von August 2013 bis September 2018 am Institut für Organische Chemie der Julius-Maximilians-Universität Würzburg angefertigt. Teile dieser Arbeit wurden bereits veröffentlicht in: M. Vogt, R. Buschmann, S. Toksabay, M. Schmitt, M. Schwab, M. Bode, A. Krueger, „Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag (111),“ J. Phys. Chem. C 2019, 123, 5469–5478.” Weitere Veröffentlichung: E. Reusch, D. Kaiser, D. Schleier, R. Buschmann, A. Krüger, T. Hermann, B. Engels, I. Fischer, P. Hemberger, „Pentadiynylidene and its Methyl-Substituted Derivates: Threshold Photoelectron Spectroscopy of R1-C5-R2 Triplet Carbon Chains,“ J. Phys. Chem. A 2019, 123, 2008–2017.” Acknowledgements First and foremost I would like to thank my supervisor Prof. Anke Krüger for the opportunity to complete this research in her group. Her knowledge, guidance and enthusiasm for science was invaluable. I would also like to express my sincere gratitude to the employees of the Organic Chemistry institute: I am indebted to Dr Matthias Grüne, Dr Ann-Christin Pöppler, Patricia Altenberger and Elfriede Ruckdeschel for advice when measuring and interpreting NMR spectra, as well as Dr Michael Büchner, Juliane Adelmann, Fritz Dadrich and Antje Heckmann for mass measurements. I would especially like to thank Liselotte Michels and Sabine Timmroth for the elemental analysis measurements, Matthias Fromm for the support in the teaching lab, Jonathan Landeck for his glassblowing expertise, Michael Ramold and Markus Braun for their help with repairs and the steady dry ice supply, Bernd Brunner for his help with IT issues and everyone at the chemical store. The members of the Krueger group deserve a special mention, for the enjoyable working environment and their intellectual and emotional support. Thanks to Stefan Wachtler and Julia Puck, for being very pleasant fume hood partners and to Dr Yvonne Kirchwehm, from whom I learnt a lot about tribenzotriquinacene research. Dr Sarah Schweeberg and Julia Puck shared my enthusiasm for baking and I am grateful for the regular supply of cake! Thanks to all group members, past and present: Dr Johannes Auerswald, Dr Patrick Betz, Christian Bauer, Dr Peter Buschmann, Dr Steffen Heyer, Dr Benjamin Kiendl, Stefan Kupka, Dr Daniel Lang, Viktor Merz, Andreas Muzha, Dr Sara Ranjbar, Lena Roos, Dr Sarah Schweeberg, Sinem Toksabay, Sebastian Vettermann, Dr Thilo Waag and Stefan Wachtler. I’m very grateful for the financial support from the DFG GRKs 1221 and 2112, as well as the members for the stimulating disscusions and providing fresh perspective on my work. I would like to thank Julia Merz from the group of Prof. Marder for her support with borylation and SUZUKI coupling reactions, as well as Dr Alexandra Friedrich, Carsten Paulmann (PETRA III synchotron), Dr Krzysztof Radacki and Johannes Krebs for the x-ray crystal structure determination. Collaborating with Prof. Matthias Bode, Matthias Vogt, Martin Schmitt and Markus Schwab was a rewarding experience and I am grateful for their expertise in producing high quality STM images and the many fruitful discussions about the orientation of molecules on a metal surface. Thanks to Astrid Kudzus from the group of Prof. Würthner for gradient sublimation in the preparation of samples for STM analysis. I had the pleasure of supervising many students and I would like to take the opportunity to mention the valuable contributions of the apprentices Maria Son, Felix Mitesser and Julian Herbert, as well as the students Iris Bodenschlägel, Marian Deutsch, Thomas Hertle, Michael Hofmann, Lena Roos and Markus Voelckel. Outside of the lab I would like to thank my church family, particularly the small groups I was part of, whose prayers and encouragement helped when I most needed it. Rowing also provided a valuable break from lab work and I enjoyed the company of the students at ARCW, both off and on the water. Lastly, I am grateful for the support of my parents Peter and Stella and brother Matthew, without whom I would not be where I am today. Last but definitely not least, I would like to thank my loving, supportive, encouraging and patient husband Peter, who often helped me put things into perspective. Table of Contents 1 Introduction ................................................................................................................ 1 1.1 Carbon – a plethora of allotropes ................................................................................. 1 1.2 Graphene ...................................................................................................................... 1 1.3 Molecular electronics ................................................................................................... 2 1.3.1 Tuning the electronic properties of graphene............................................................... 3 1.3.2 Holey graphene ............................................................................................................ 3 1.3.3 Defective graphene....................................................................................................... 4 1.3.4 Fluorinated graphene .................................................................................................... 6 1.4 Nanographenes ............................................................................................................. 6 1.4.1 Extension of polyaromatic hydrocarbons .................................................................... 6 1.4.2 Fluorinated polyaromatic hydrocarbons .................................................................... 15 1.4.3 Introducing strain in nanographenes .......................................................................... 17 1.4.4 Tribenzotriquinacene as a defective core ................................................................... 21 1.5 Tribenzotriquinacene crystal structure ....................................................................... 22 1.6 Tribenzotriquinacene synthesis .................................................................................. 23 1.7 Tribenzotriquinacene functionalisation ...................................................................... 25 1.8 Extended TBTQs ........................................................................................................ 29 2 Aims ........................................................................................................................... 31 3 Results and Discussion ............................................................................................. 34 3.1 Influence of the functionalisation of the centro-position – STM investgation of TBTQ ......................................................................................................................... 34 3.2 Functionalisation of the ortho-position – synthesis of fluorinated TBTQs ............... 50 3.2.1 Monofluorinated TBTQs ............................................................................................ 50 3.2.2 Trifluorinated TBTQs ................................................................................................ 53 3.3 Funtionalisation of the ortho-position – synthesis of phenanthreno-TBTQs and study of their stacking arrangements ................................................................................... 72 3.3.1 Summary of previous work ........................................................................................ 72 3.3.2 Introduction of a third phenanthrene group via KNOEVENAGEL reaction .................. 74 3.3.3 Synthesis of dibenzophenanthrenotriquinacene (DBPTQ, 102) ................................ 75 3.3.4 Alternative approach to phenanthrene group introduction: a simplified model system82 3.3.5 Synthesis of benzodiphenanthrenotriquinacene (BDPTQ, 103) ................................ 85 I 3.3.6 Methoxy functionalised phenanthrenes ..................................................................... 91 3.3.7 tert-butyl functionalised phenanthrenes ................................................................... 108 3.4 Functionalisation of the meta position – Borylation and extension of TBTQ with pheanthrene moieties ................................................................................................ 115 4 Summary and Outlook .......................................................................................... 132 4.1 Influence of the functionalisation of the centro-position: STM investigation of TBTQs ...................................................................................................................... 132 4.2 Functionalisation
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