New Electron-Deficient Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed C–C Coupling and Core Halogenation–Cyanation Dissertation zur Erlangung des naturwissenschaftlichen Doktorgrades der Julius-Maximilians-Universität Würzburg vorgelegt von Sabine Seifert aus Marktredwitz Würzburg 2017 ii Eingereicht bei der Fakultät für Chemie und Pharmazie am: 18.10.2017 Gutachter der schriftlichen Arbeit: 1. Gutachter: Prof. Dr. Frank Würthner 2. Gutachter: Prof. Dr. Anke Krüger Prüfer des öffentlichen Promotionskolloquiums: 1. Prüfer: Prof. Dr. Frank Würthner 2. Prüfer: Prof. Dr. Anke Krüger 3. Prüfer: Prof. Dr. Ingo Fischer Datum des öffentlichen Promotionskolloquiums: 15.12.2017 Doktorurkunde ausgehändigt am: _________________________ iii iv Abbreviations abs absorbance/absorption Ac acetyl Ar aryl ap applied a.u. arbitrary unit (I)CT (intramolecular) charge transfer CV cyclic voltammetry dba dibenzylideneacetone DBN 1,5-diazabicyclo[4.3.0]non-5-ene DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (TD-)DFT (time-dependent) density functional theory DIPEA diisopropylethylamine DMAP 4-dimethylaminopyridine DMF dimethylformamide DMSO dimethyl sulfoxide dppf 1,1'-bis(diphenylphosphino)ferrocene em emission ESI electrospray ionization ex excitation Fc+/Fc ferrocenium/ferrocene redox couple fl fluorescence iPr iso-propyl HOMO highest occupied molecular orbital HPLC high performance liquid chromatography HR high-resolution I intensity L ligand LUMO lowest unoccupied molecular orbital PADI polycyclic aromatic dicarboximide PAH polycyclic aromatic hydrocarbon v PBI perylene bisimide Ph phenyl PIFA phenyliodine bis(trifluoroacetate) pin pinacolato (T)M (transition) metal MALDI matrix-assisted laser desorption/ionization Me methyl MO molecular orbital MS mass spectrometry m/z mass-to-charge ratio NBI naphthalene bisimide NBS N-bromosuccinimide n-Bu n-butyl NI naphthalene imide NIR near infra-red NMR nuclear magnetic resonance OFET organic field effect transistor OLED organic light emitting diode OTf triflate ox oxidation/oxidant QBI quarterrylene bisimide red reduction/reductant rt room temperature SEC spectroelectrochemistry SPhos 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl SWV square wave voltammetry TBAF tetrabutylammonium fluoride TBAHFP tetrabutylammonium hexafluorophosphate TBI terrylene bisimide tBu tert-butyl THF tetrahydrofuran TIPS triisopropylsilyl TMS trimethylsilyl or tetramethylsilane Tol tolyl vi Ts tosyl UV ultra violet V potential Vis visible vt virtual vii Table of Contents Chapter 1 Aim of the Thesis ..................................................................................................... 1 Chapter 2 Literature Survey ...................................................................................................... 6 2.1 C–C Coupling Reactions for the Construction of Polycyclic Aromatic Hydrocarbons . 6 2.1.1 Introduction .............................................................................................................. 6 2.1.2 Mechanistic Aspects ................................................................................................ 7 2.1.3 Application of C–C Coupling Reactions for the Construction of PAHs ............... 13 2.2 Polycyclic Aromatic Dicarboximides ........................................................................... 22 2.2.1 Introduction ............................................................................................................ 22 2.2.2 Polycyclic Aromatics containing Six-Membered Dicarboximides ........................ 23 2.2.3 Polycyclic Aromatics containing Five-Membered Dicarboximides ...................... 45 Chapter 3 Results and Discussion ........................................................................................... 49 3.1 Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Naphthalene Dicarboximides with Pyrene ......................................................................................................................... 49 3.1.1 Introduction ............................................................................................................ 49 3.1.2 Synthesis of Mono-, Di- and Tetra-Naphthalimide-Substituted Pyrenes .............. 50 3.1.3 Optical Properties ................................................................................................... 52 3.1.4 Electrochemical Properties .................................................................................... 57 3.1.5 Conclusion ............................................................................................................. 59 3.2 Palladium-Catalyzed C–C Coupling Cascade Reactions: An Efficient Route to Electron-Poor Polycyclic Aromatic Dicarboximides on the Nanoscale ............................. 60 3.2.1 Introduction ............................................................................................................ 60 3.2.2 Synthesis and Mechanistic Rationale ..................................................................... 61 3.2.3 Structural Elucidation ............................................................................................ 66 3.2.4 Optical and Electrochemical Properties ................................................................. 68 3.2.4 Conclusion ............................................................................................................. 73 3.3 Base-Selective Six- versus Five-Membered Ring Annulation in Palladium-Catalyzed C–C Coupling Cascade Reactions: Synthesis of New Polycyclic Aromatic Dicarboximides and Mechanistic Rationale .................................................................................................. 74 3.3.1 Introduction ............................................................................................................ 74 3.3.2 Synthesis and Mechanistic Rationale ..................................................................... 75 viii 3.3.3 Structural Elucidation ............................................................................................. 80 3.3.4 Optical and Electrochemical Properties ................................................................. 83 3.3.5 Conclusion .............................................................................................................. 88 3.4 An Ambient Stable Core-Substituted Perylene Bisimide Dianion ................................ 89 3.4.1 Introduction ............................................................................................................ 89 3.4.2 Synthesis ................................................................................................................. 90 3.4.3 Structural Elucidation ............................................................................................. 91 3.4.4 Electrochemical Studies ......................................................................................... 96 3.4.5 Conclusion ............................................................................................................ 100 Chapter 4 Summary ............................................................................................................... 101 Chapter 5 Zusammenfassung ................................................................................................. 108 Chapter 6 Experimental Part .................................................................................................. 115 6.1 Materials and Methods ................................................................................................ 115 6.2 Synthesis and Characterization .................................................................................... 119 6.2.1 Synthesis of Aryl Boronic Acid Pinacol Esters .................................................... 119 6.2.2 Synthesis of Naphthalimide-Substituted Pyrenes ................................................. 123 6.2.3 Synthesis of Six-Membered Ring Annulated Systems by C–C Coupling Cascade Reactions ................................................................................................ 127 6.2.4 Synthesis of Five-Membered Ring Annulated Systems by C–C Coupling Cascade Reactions ................................................................................................ 133 6.2.5 Synthesis of Core-Functionalized Perylene Bisimides ......................................... 139 6.3 Single Crystal Data ...................................................................................................... 142 Appendix ............................................................................................................................... 146 Literature ............................................................................................................................... 147 ix x Chapter 1 Aim of the Thesis Chapter 1 Aim of the Thesis Nanoscience is an emergent field of interdisciplinary science combining research fields of chemistry, physics, materials science and biology and will probably evolve to one of the key- technologies of the 21st century. This area of research is concerned with the exploration of materials on the scale of few nanometers up to 100 nm and has great influence on nearly all economic sectors such as optics, electronics, information technology, mechanical engineering, health and environmental science.[1] Materials of this size are either comparatively large single molecules or defined assemblies of small molecules like they exist in nature since the origin