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1 University of Hull Dipyrrin Complexes and Their Uses UNIVERSITY OF HULL DIPYRRIN COMPLEXES AND THEIR USES AS SELF ASSEMBLING MATERIALS Being a thesis submitted for the Degree of Doctor of Philosophy in the University of Hull By Michael Benstead, MChem(hons) December 2010 1 Acknowledgements Firstly, my thanks go to my supervisors Ross Boyle and Georg Mehl for their continued help and support throughout this project. Thanks also to Julie Haley and Rob Lewis for their help with DSC, HPLC and NMR. Many thanks go to lab members of C120 and C302 both past and present for their help and interesting banter throughout my time in the lab. In particular Chris Welch, Cristina Alonso and Francesca Giuntini for their help with various reactions and NMR interpretation. Lastly, many thanks to both my parents and my lovely wife Michelle without whose support this work would not be possible as we look forward to the arrival of baby Benstead, who will have to read this at some point I‘m sure. 2 Abstract Several series of BODIPYs bearing mesogenic substituents were synthesised and their fluorescence and liquid crystal properties were characterized. Each compound prepared consisted of one BODIPY fluorophore and one, two or three mesogenic units based primarily on a cyanobiphenyl core. Initially, the mesogens were attached to the pyrrolic positions of the fluorophore, but it was found that mesogen attachment at the BODIPY 8- phenyl ring gave an increased preference for mesophase formation due to the molecules having a more ‗rod-like‘ (calamitic) shape. For several of the compounds, a monotropic nematic phase was exhibited, however, no layered phase (e.g. smectic) was observed. Several linker groups between the mesogenic unit and the fluorophore were investigated and it was found that linear linker groups (e.g. ethynyl) had a greater preference for liquid crystal phase formation when compared to non-linear linker groups (e.g. triazole). Two series of di-mesogenic compounds were prepared and a significant stabilisation of the nematic phase was observed when compared to the mono-mesogenic analogues. The compounds bearing the mesogenic units on the 8-phenyl ring were prepared by metal- catalyzed couplings and each series consisted of three compounds with increasing alkyl substitution on the bipyrrolic core of the BODIPY. This resulted in a progressive increase in fluorescence quantum yield of the compounds in each series due to increased rotational restriction of the 8-phenyl ring along with a concurrent decrease in nematic phase stability. This permitted the observation of a structure-property relationship between nematic phase stability and fluorescence intensity. A BODIPY with significantly red- shifted fluorescence was also prepared and three mesogenic units were attached to this compound. Temperature dependant fluorescence measurements were taken in order to observe any relationship between fluorescence and degree of molecular ordering (e.g. nematic phase fluorescence compared to isotropic liquid fluorescence) and several of the compounds were dissolved in a commercial nematic liquid crystal and incorporated into a twisted nematic cell in order to observe the affect that molecular alignment (induced by an electric field) had on the fluorescence. 3 Table of contents: Table of figures: ................................................................................................................ 7 Table of schemes: ............................................................................................................ 16 Table of schemes: ............................................................................................................ 16 List of abbreviations ....................................................................................................... 20 List of abbreviations ....................................................................................................... 20 Chapter 1: BODIPYs as components in novel light active materials ......................... 22 1. Dipyrrins .................................................................................................................. 22 1.1 Structure ............................................................................................................. 22 1.2 Properties of dipyrrin complexes ....................................................................... 23 1.2.1 Fluorescence properties of dipyrrin complexes ........................................... 23 1.2.2 Electrochemical properties of dipyrrin complexes ...................................... 24 1.3 Synthesis ............................................................................................................. 24 1.3.1 Condensation of pyrroles ............................................................................. 25 1.3.2 Oxidation of dipyrromethanes ..................................................................... 28 2. Borondifluorodipyrrins (BODIPYs) ..................................................................... 29 2.1 Structure ............................................................................................................. 30 2.2 Properties of BODIPYs ...................................................................................... 30 2.3 Synthesis of BODIPYs ....................................................................................... 34 2.4 Fluorescence control of BODIPYs by modification of the 8-aryl group ......... 36 2.4.1 Photoinduced electron transfer (PeT) ......................................................... 36 2.5 Metal-catalyzed reactions of BODIPYs ............................................................. 40 2.6 Condensation reactions of 3,5-dimethyl-BODIPYs .......................................... 44 2.7 Aza-BODIPYs..................................................................................................... 46 2.8 Energy transfer cassettes ................................................................................... 48 2.8.1 Through-space energy transfer cassettes..................................................... 48 2.8.2 Through-bond energy-transfer cassettes ..................................................... 57 2.9 BODIPY-based energy-transfer arrays as light harvesting materials in electrooptic devices ................................................................................................... 80 2.9.1 Dye-sensitized solar cells ............................................................................. 80 4 2.9.2 Bulk heterojunction solar cells .................................................................... 85 2.10 BODIPYs as laser dyes .................................................................................... 88 2.10.1 Laser activity of dye-doped polymeric matrices based on commercial BODIPY derivatives .............................................................................................. 92 2.10.2 Laser activity of BODIPYs in dye-doped liquid crystals ......................... 100 2.11 Polymers incorporating BODIPY fluorophores ........................................... 102 2.11.1 Polymerisation through the BODIPY core .............................................. 102 2.11.2 Polymerisation through F-substitution .................................................... 110 2.11.3 Polymerisation through the BODIPY meso-position ............................... 112 2.11.4 Polymerisation through metal-complexation and conducting polymers . 116 3. Supramolecular assemblies .................................................................................. 119 3.1 Principles of self-assembly............................................................................... 119 3.2 Self-assembly of liquid crystalline materials................................................... 120 3.2.1 Thermotropic liquid crystals ...................................................................... 120 3.2.2 Lyotropic liquid crystals ............................................................................ 123 3.2.3 Mesogenic BODIPYs and their self-assembling properties....................... 124 4. Conclusions ............................................................................................................ 132 Chapter 2: Aims ............................................................................................................ 135 3.1. Introduction ........................................................................................................ 138 3.2. Results and discussion ....................................................................................... 141 3.2.1 Synthesis ........................................................................................................ 141 3.2.2 Melting behaviour ......................................................................................... 154 3.2.3 Fluorescence ................................................................................................. 159 3.3. Conclusions ......................................................................................................... 161 Chapter 4: BODIPYs bearing mesogenic units attached to the 8-phenyl ring ....... 163 4.1. Introduction ........................................................................................................ 163 4.2. Results and discussion ....................................................................................... 165 4.2.1 Synthesis ........................................................................................................ 165 4.2.2
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