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Silicon Containing Mesogen Building Blocks - Synthesis, Characterization and Application in Silane and Siloxane Self-Assembly

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Silicon Containing Mesogen Building Blocks - Synthesis, Characterization and Application in Silane and Siloxane Self-Assembly TECHNISCHE UNIVERSITÄT MÜNCHEN Institut für Siliciumchemie, WACKER-Lehrstuhl für Makromolekulare Chemie Silicon Containing Mesogen Building Blocks - Synthesis, Characterization and Application in Silane and Siloxane Self-Assembly Dipl.-Chem. Paul Heinz Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigten Dissertation. Vorsitzende: Univ.-Prof. Dr. Sevil Weinkauf Prüfer der Dissertation: 1. Univ.-Prof. Dr. Dr. h.c. Bernhard Rieger 2. Univ.-Prof. Dr. Klaus Köhler Die Dissertation wurde am 14.02.2012 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 08.05.2012 angenommen. “If I would have asked them what they want, they would have said faster horses” (Henry Ford, 1863-1947) Acknowledgements This dissertation was prepared at the Institute of Silicon Chemistry and the WACKER-Chair of Macromolecular Chemistry at the Technische Universität München in the period between August 2007 and March 2011 under the supervision of Prof. Dr. Dr. h.c. Bernhard Rieger. Prior to describing the topic and the results, I would like to express my deepest gratitude to all people who contributed to the success of this work. In particular, I would like to thank Prof. Rieger for the opportunity to pursue my research at his working group and giving me every ‘degree of freedom’ in defining the topic and following new ideas. I also want to thank him for his patience, numerous fruitful discussions, and for his open door and attentive ear to any kind of questions. Furthermore I want to thank WACKER Chemie AG for financial support through granting me the WACKER Presidential Science Award. This work would not have been possible without various internal and external cooperation partners. Therefore I would like to thank the following people: Prof. Dr. Christine M. Papadakis from the Physics Department of the TU München for providing the possibility to perform SAXS and GISAXS measurements at the synchrotron radiation source HASYLAB at the ‘Deutsches Elektronen Synchrotron’ (DESY) in Hamburg and also for many discussions and her invaluable contribution to our publication in ChemPhysChem. Prof. Dr. Sevil Weinkauf and Dr. Marianne Hanzlik from the Electron Microscopy Department of the TU München, for many TEM and SEM measurements, valuable discussions and especially for hosting our STM device at their premises. Dr. Jürgen Heindl and Dr. Matthias Rodewald from JEOL Germany for SEM and TEM measurements. PD Dr. Hubert Rauscher, Dr. Giacomo Ceccone and Dr. Douglas Gilliland from the Institute for Health and Consumer Protection, DG Joint Research Centre, European Commission in Ispra (VA, Italy) for their assistance in XPS, DLS, and Ellipsometry measurements. Also many thanks to Francesco Fumagalli for hosting me during two visits in Ispra and for lots of experiments on the plasma reactor. Natürlich möchte ich mich auch bei meinen Kollegen am Institut für Siliciumchemie und am WACKER-Lehrstuhl für die tolle Zeit, die ich mit Ihnen in den letzten Jahren verbringen durfte, bedanken. Ganz besonders bedanke ich mich bei Dr. Carsten Troll und Dr. Sergei Vagin für ihre Unterstützung in technischen, administrativen und wissenschaftlichen Fragen. Weiterhin danke ich Aleksandra Jonovich, Katia Rodewald und Dr. Uwe B. Seemann für zahllose Messungen an der GPC. Sanna Zimmer gilt mein besonderer Dank für ihre Hilfe beim Drucken, Binden und Einreichen der Arbeit. Und schließlich auch vielen Dank an meine ehemaligen Laborkollegen Dr. Robert Luxenhofer, Dr. Michael Reif, Tobi van Deisner, Abdussalam Qaroush und Konrad Hindelang für die tolle Arbeitsatmosphäre im Labor. Auch bei meinen ‚Masteranden‘ und ‚Diplomanden‘ sowie bei meinen Forschungs- praktikanten möchte ich mich für die gute Zusammenarbeit und ihre zahlreichen Resultate, ohne die weder diese Arbeit, noch die Publikationen möglich waren. Im Einzelnen waren das (in chronologischer Reihenfolge): Sascha Erhardt, Annemarie Frey, Linus Schulz, Michael Wegener, Konrad Hindelang, Christian Anger und Florian Golling. Ich wünsche Euch alles Gute auf dem weiteren Weg! Ganz besonderer Dank gilt einer ganz speziellen Kollegin und gleichzeitig meiner Partnerin. Danke Moni für Deine Unterstützung und für Deine unendliche Geduld in allen Lebenssituationen. Deine Liebe und Treue bedeutet mir alles! Vielen Dank auch für die vielen Wochenenden die Du während dem Schreiben der Arbeit geopfert hast um mir den Rücken freizuhalten - wir werden alles nachholen! Natürlich auch vielen Dank fürs Lesen und Korrigieren. Zuletzt bedanke ich mich ganz herzlich bei meiner Familie. Ganz besonders möchte ich meinen Eltern danken die mich all die Jahre - nicht nur finanziell - unterstützt haben. Vielen Dank auch meiner Schwester dass Sie mir zwei so tolle Patenkinder geschenkt hat. Ich wollte nie etwas anderes als Euch stolz zu machen! Table of Contents i Table of Contents 1 Introduction ............................................................................................................. 1 2 Theoretical Background ......................................................................................... 7 2.1 Supramolecular Chemistry and Self-Assembly Phenomena ................................ 7 2.1.1 Different Forms of Single Molecule Self-Assembly .................................. 11 2.2 Silicon Containing Oligomers and Polymers...................................................... 15 2.2.1 Basic Materials ........................................................................................... 15 2.2.2 Polysiloxanes .............................................................................................. 17 2.2.3 Three Dimensional Siloxane Structures ..................................................... 21 2.2.4 Polysilanes .................................................................................................. 25 2.2.5 Polysilane Networks ................................................................................... 31 2.2.6 Defined Si-based Polyhedra ........................................................................ 33 3 Objectives .............................................................................................................. 37 4 Mesogen Library ................................................................................................... 43 4.1 Introduction ......................................................................................................... 43 4.2 Synthesis Strategy ............................................................................................... 45 4.2.1 Metalated Mesogens for the Nucleophilic Substitution on Chlorosilanes .. 46 4.2.2 Mesogens with Unsaturated Functional Groups ......................................... 48 4.3 Summary ............................................................................................................. 54 ii 5 Bi and Tetramesogens with Silicon Containing Linkers ................................... 57 5.1 Introduction ......................................................................................................... 57 5.2 Synthesis .............................................................................................................. 59 5.2.1 Bimesogens ................................................................................................. 59 5.2.2 Tetramesogens ............................................................................................. 62 5.3 Properties of Bulk Materials ............................................................................... 64 5.3.1 Thermal Properties and Formation of Mesophases ..................................... 64 5.3.2 Structures of Bulk Materials ....................................................................... 75 5.4 Morphologies and Structures of Thin Films ....................................................... 80 5.4.1 Surface Structures Visualized by AFM ....................................................... 80 5.4.2 Determination of Thin Film Characteristics ................................................ 83 5.5 Summary ............................................................................................................. 87 6 Silicon Based Polymers ......................................................................................... 91 6.1 Introduction ......................................................................................................... 91 6.2 Synthesis of Monomers ....................................................................................... 93 6.2.2 Styrene-Based Monomers ........................................................................... 95 6.3 Wurtz-Type Reductive Polymerizations ............................................................ 104 6.4 Determination of Polymer Characteristics ........................................................ 110 6.4.1 Polymers from Saturated Monomers ......................................................... 110 6.4.2 Polymers from Unsaturated Monomers .................................................... 114 6.5 Self-Assembly on Surfaces ............................................................................... 126 6.6 Effect of Pyrolysis on Nanostructures ............................................................... 135 6.7 Homogeneously Nanostructured Films by Plasma Treatment .......................... 140 6.8 Summary ..........................................................................................................
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