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Synthetical Engineering of Supramolecular Properties of Large Polycyclic Aromatic Hydrocarbons

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Synthetical Engineering of Supramolecular Properties of Large Polycyclic Aromatic Hydrocarbons Wasserfallen Daniel Synthetical Engineering of Supramolecular Properties of Large Polycyclic Aromatic Hydrocarbons Mainz 2006 Dekan: Prof. Dr. Peter Langguth 1. Berichterstatter: Prof. Dr. Klaus Müllen 2. Berichterstatter: Prof. Dr. Rudolf Zentel Tag der mündlichen Prüfung: xx. xx. 2006 i ii Die vorliegende Arbeit wurde in der Zeit vom März 2002 bis November 2005 im Max- Planck-Institut für Polymerforschung unter der Leitung von Herrn Prof. Dr. K. Müllen durchgeführt. Ich danke Herrn Prof. Dr. K. Müllen sowohl für seine wissenschaftliche und persönliche Unterstützung als auch für seine stetige Diskussionsbereitschaft. iii iv Dedicated to my mother "Die Schwierigkeiten scheinen nur da zu sein, um überwunden zu werden." Hoffmann von Fallersleben (1798-1874) v vi Contents 1 Introduction.............................................................................................................. 1 1.1 Benzene and Aromaticity................................................................................... 1 1.2 Polycyclic Aromatic Hydrocarbons................................................................... 2 1.3 The "Aromatic Sextet" and Fully Benzenoid PAHs.......................................... 3 1.4 Synthesis of PAHs ............................................................................................. 6 1.4.1 Cyclotrimerization of Diphenylacetylenes ................................................ 8 1.4.2 Intramolecular Diels-Alder Reaction......................................................... 9 1.4.3 Intermolecular Diels-Alder Reaction......................................................... 9 1.5 Supramolecular Properties of PAHs................................................................ 11 1.5.1 Discotic Liquid Crystals .......................................................................... 12 1.5.2 Monolayers of PAHs............................................................................... 16 1.5.3 Intracolumnar Charge Carrier Transport ................................................. 18 1.7 Devices Based on Discotic Organic Materials ................................................ 20 1.8 References........................................................................................................ 22 2 Motivations and Objectives .................................................................................. 29 2.1 References........................................................................................................ 31 3 Influence of Hydrogen-Bonds on the Supra-molecular Properties of Hexa- peri-hexabenzo-coronenes ..................................................................................... 33 3.1 Hydrogen-bonds .............................................................................................. 34 3.2 Desymmetrized HBCs..................................................................................... 36 3.3 Engineering the Properties of HBC via Hydrogen-Bonding ........................... 37 3.3.1 Synthesis of Carboxy-functionalized HBCs............................................ 38 3.3.2 Synthesis of Covalently Linked Dyads.................................................... 42 3.3.3 Bulk Properties of Carboxy-functionalized HBCs and Dyads ................ 43 3.3.3.1 Differential Scaning Calorimetry (DSC) ............................................ 43 3.3.3.2 2D-WAXS .......................................................................................... 44 3.3.3.3 Solid-State NMR of Carboxy-functionalized HBCs .......................... 50 3.3.4 Properties on Surfaces ............................................................................. 53 3.3.5 Discussion................................................................................................ 55 3.4 Inducing processability.................................................................................... 59 3.4.1 Synthesis.................................................................................................. 60 3.4.2 Bulk Properties........................................................................................ 62 3.4.2.1 DSC..................................................................................................... 62 3.4.2.2 2D-WAXS .......................................................................................... 63 3.4.3 Discussion................................................................................................ 66 3.4.4 Conclusions.............................................................................................. 69 3.6 References........................................................................................................ 69 4 "Supernaphthalene".............................................................................................. 75 4.1 Synthesis .............................................................................................................. 78 4.1.1 2,2'-Diethinylbiphenyl ............................................................................. 78 4.1.2 Tetraphenylcyclopentadienone Derivatives............................................. 81 4.1.3 Intramolecular Cyclodehydrogenation.................................................... 84 4.1.3.1 C72-(C8,2)8 .......................................................................................... 86 4.1.3.2 C72-(C12)8 ........................................................................................... 88 4.1.3.3 C72-(Ph-C12)8 ..................................................................................... 89 vii 4.2 Closer Investigation on C72-(C12)8 ......................................................................91 4.2.1 UV/vis ......................................................................................................91 4.2.2 HPLC........................................................................................................92 4.2.3 Photoluminescence Experiments..............................................................95 4.2.4 Polarized Optical Microscopy..................................................................97 4.2.5 2D-WAXS................................................................................................98 4.2.6 Conclusions ..............................................................................................99 4.3 Verification of the MALDI-TOF MS Data ........................................................100 4.3.1 C72-(C12)8...............................................................................................100 4.3.2 Investigations on Other Extended PAHs................................................106 4.3.3 Discussion ..............................................................................................109 4.3.4 Conclusions ............................................................................................117 4.4 Investigations on Workup Procedures................................................................118 4.4.1 Preparative Column Chromatography....................................................118 4.4.2 Influencing the Retention Times............................................................119 4.5 Influencing the Electronic and Solubility Properties of the Oligophenylene Precursor.............................................................................................................124 4.5.1 Removal of Alkyl Side-Chains ..............................................................124 4.5.2 Changing the Oligophenylene Substitution Pattern ...............................128 4.5.3 Conclusions ............................................................................................142 4.6 Preplanarization of the Oligophenylene Precursor at the Outer Rim................143 4.6.1 C74, C76, C76-(t-Bu).............................................................................143 4.6.2 Specific Synthesis of Panels...................................................................151 4.7 Preplanarization in the Center of the Oligophenylene Precursor ......................158 4.7.1 Inducing Solubility by Distortion of the Aromatic Core Component and Bulky Substituents ...........................................................................160 4.7.2 C72-(C12)8-(t-Bu)2 ..................................................................................163 4.7.2.1 Synthesis............................................................................................164 4.7.2.2 MALDI-TOF MS ..............................................................................166 4.7.2.3 1H NMR Spectroscopy......................................................................167 4.7.2.4 Electronic Spectroscopy....................................................................168 4.7.3 Improving the Solubility Properties by Bulky Alkyl Substituents.........170 4.7.4 C72-(C12)4-(C14,10)4-(t-Bu)2 ....................................................................171 4.7.4.1 Synthesis............................................................................................171 4.7.4.2 MALDI-TOF MS ..............................................................................172 4.7.4.3 1H NMR Spectroscopy......................................................................173 4.7.4.4 2D NMR Spectroscopy .....................................................................177 4.7.4.5 Theoretical Calculations....................................................................180 4.7.4.6 Electronic Spectroscopy....................................................................183
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