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Synthesis, Properties and Application of Polyphenylene Phosphonium Salts

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Synthesis, Properties and Application of Polyphenylene Phosphonium Salts Synthesis, Properties and Application of Polyphenylene Phosphonium Salts Dissertation zur Erlangung des Grades Doktor der Naturwissenschaften im Promotionsfach Makromolekulare Chemie Am Fachbereich Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität in Mainz vorgelegt von Ralf Moritz geboren in Hutthurm Mainz, 2015 Dekan: 1. Berichterstatter: 2. Berichterstatter: Tag der Mündlichen Prüfung: 13. April 2015 Die vorliegende Arbeit wurde am Max Planck Institut für Polymerforschung in Mainz im Zeitraum vom Februar 2011 bis Februar 2015 angefertigt. Danksagung Ich danke Herrn Prof. Dr. Klaus Müllen herzlich für das spannende Thema meiner Arbeit, welches volle Begeisterung für die Chemie der Polyphenylen-Elektrolyte bei mir entfacht hat durch sein stetes Interesse und Motivation. Ich möchte mich besonders für seine hervorragende wissenschaftliche Betreuung und für seine unterstützenden Ratschläge hinsichtlich jeglicher persönlicher Anliegen bedanken. Eine Vielzahl weiterer Personen haben das Entstehen dieser Arbeit unterstützt in einer freundlichen und kommunikativen Atmosphäre: Ich danke meinen Laborkollegen René Stangenberg, Felix Hinkel, Guang Zhang, Thi-Thanh- Tam Nguyen, Brenton Hammer, Katharina Bücher und Sascha Pietruska für die vielen interessanten Gespräche fachlicher und privater Natur. Die zahlreichen Gelegenheiten zum Ideenaustausch haben die Forschungsprojekte maßgeblich vorangetrieben und die lockeren Plaudereien gestalteten die Zeit im Labor stets kurzweilig. Besonders herzlicher Dank gebührt Cornelia Beer und Patrizia Schiel dafür, dass sie mich bei der Synthese und Aufarbeitung oft unterstützt und als guter Geist die vorbildliche Ordnung in unserem Labor gewahrt haben. Meinem Vorgänger David Türp danke ich besonders für seine engagierte und gute Unterstützung bei meinem Start ins MPIP-Leben. Manfred Wagner danke ich für die vielen interessanten Gespräche und Lektionen über die Möglichkeiten der NMR sowie unvergesslichen Momenten des Triumphes auf dem Fußballplatz. Meinem Projektleiter Martin Baumgarten danke ich für die gute Betreuung und das gründliche Lesen dieses Manuskripts. Stefan Türk danke ich für die vielen Analysen meiner Proben mittels MALDI-TOF und seinen schier unglaublich scheinenden Anekdoten über Modell-Eisenbahnbau und Minigolf. Ich danke Lukas Zöphel, Anne Pfisterer, Oliver Dumele, Thi-Thanh-Tam Nguyen, Sebastian Preiss, Jakob Wudarczyk und Uliana Beser für die wunderbare Stimmung in unserem Büro. Herzlich danke ich auch allen Mitgliedern dieses Arbeitskreises für die wunderbare gemeinsame Zeit, den guten Zusammenhalt und den vielen schönen gemeinsamen Erlebnissen. Ganz herzlich danke ich meinen Eltern Annelie Moritz und Engelbert Moritz, die stets an mich geglaubt und mich immer mit allen Kräften unterstützt haben. Schließlich danke ich von ganzem Herzen Minh-Thuy Pham dafür, dass sie immer für mich da ist. Table of Contents List of Abbreviations .......................................................................................................................1 Chapter 1 - Introduction ...............................................................................................................3 1.1 The Classiness of Monodisperse Materials ..............................................................................3 1.2 Dendrimers ...................................................................................................................................4 1.3 Polyphenylene Dendrimers ........................................................................................................8 1.4 Synthesis of Polyphenylene Dendrimers .................................................................................9 1.5 General Properties of Polyphenylene Dendrimers .............................................................. 11 1.6 Ions, Salts and Electrolytes...................................................................................................... 14 1.7 Dielectric Spectroscopy ........................................................................................................... 19 Literature ......................................................................................................................................... 20 Chapter 2 - Motivation ............................................................................................................... 22 Chapter 3 - Synthesis of Dendronized Polyphenylene Cations ............................... 26 3.1 Introduction .............................................................................................................................. 26 3.2 Ethynyl-Functionalized Tetraphenylphosphonium Core ................................................... 28 3.3 Increase of Cation Size by Divergent Dendritic Growth ..................................................... 31 3.4 Divergent Dendritic Growth towards higher-generation Cations .................................... 38 3.5 Surface Functionalization ....................................................................................................... 41 3.6 Synthesis of Aryl-Triazole Hybrid Phosphonium Dendrimers ........................................... 50 3.7 Discussion and Outlook .......................................................................................................... 56 Literature ......................................................................................................................................... 63 Chapter 4 - Physical and Chemical Properties of Dendronized Salts .................... 66 4.1 Introduction .............................................................................................................................. 66 4.2 Cation Exchange Experiments ................................................................................................ 67 4.3 Hydrodynamic Radii of Dendronized Salts ........................................................................... 74 4.4 Dielectric Spectroscopy of Dendronized Salts ..................................................................... 77 4.5 Chemical Properties of Dendronized Phosphonium Salts ................................................. 84 4.6 Discussion and Outlook .......................................................................................................... 90 Literature ......................................................................................................................................... 94 Table of Contents Chapter 5 - Application of Dendronized Benzylphosphonium Salts in the Wittig Reaction ............................................................................................................................. 96 5.1 Introduction .............................................................................................................................. 96 5.2 Divergent Synthesis of Dendronized Benzylphosphonium Salts ...................................... 98 5.3 Convergent Synthesis of Dendronized Benzylphosphonium Salts ................................... 99 5.4 Wittig Reaction of Dendronized Benzylphosphonium Salts ............................................ 104 5.5 Synthesis of Dendronized Methylphosphonium Iodide (5-28) ........................................ 110 5.6 Discussion and Outlook ........................................................................................................ 114 Literature ....................................................................................................................................... 121 Chapter 6 - Dendronized Polyelectrolytes ...................................................................... 123 6.1 Introduction ............................................................................................................................ 123 6.2 Hydrophobization of a Polycation ....................................................................................... 124 6.3 Dendritically Shielded Ionic Group at a Polycation ........................................................... 132 6.4 Discussion and Outlook ........................................................................................................ 138 Literature ....................................................................................................................................... 141 Chapter 7 – Summary and Outlook ................................................................................... 143 Chapter 8 – Experimental Part ............................................................................................. 146 8.1 Materials and Methods ......................................................................................................... 146 8.2 Syntheses ................................................................................................................................ 152 8.3 Appendix ................................................................................................................................. 198 Literature ....................................................................................................................................... 203 List of Publications ........................................................................................................................ 204 Lebenslauf ...................................................................................................................................... 205 List of Abbreviations 1 List of Abbreviations
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