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A Sheffield Hallam University Thesis Synthesis and characterisation of some solvatochromic betaine systems. MIFFLIN, Joanne Patricia Louise. Available from the Sheffield Hallam University Research Archive (SHURA) at: http://shura.shu.ac.uk/20063/ A Sheffield Hallam University thesis This thesis is protected by copyright which belongs to the author. The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the author. When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given. Please visit http://shura.shu.ac.uk/20063/ and http://shura.shu.ac.uk/information.html for further details about copyright and re-use permissions. REFERENCE ProQuest Number: 10697370 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10697370 Published by ProQuest LLC(2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 Synthesis and Characterisation of Some Solvatochromic Betaine Systems Joanne Patricia Louise Mifflin (BSc Hons) A thesis submitted in partial fulfilment of the requirements of Sheffield Hallam University for the degree of Doctor of Philosophy October 1998 £J]V CAMPUS ABSTRACT This thesis is concerned with the synthesis and characterisation of five new types of solvatochromic systems and preliminary investigations into the synthesis of some new systems involving several such chromophoric units. Confirmation of the structure of these systems was carried out by NMR (31P and !H), and mass spectral analysis, together with the results of microanalysis. The solvatochromic behaviour was investigated in detail, by dissolution in a range of solvents and measurement of their longest-wavelength absorption bands using UV/Visible spectroscopy. A range of long chain phosphoniophenyl-imidazolide betaine systems and long chain 4- N-(o-phosphoniobenzylidene) iminophenolate betaines has been prepared and their properties compared to the respective triphenylphosphonio analogues already reported in the literature. The formation of Langmuir Blodgett (LB) films by three of the amphiphilic betaines has been studied in collaboration with the University of Cranfield. The effects of annelation of a benzene ring in the triphenylphosphoniophenyl- imidazolide and -benzylidene iminophenolate systems has been investigated and the effects on the solvatochromism of the resulting compounds has been explored. As part of this study two N-hexadecylquinolinium iminophenolate betaines have been prepared and their solvatochromism compared to that of the pyridinium counterparts. LB film formation of one of the quinolinium betaines has been studied, and nonlinear optical properties observed, together with other properties that may form the basis of sensor techniques. The first solvatochromic arsonium and stibonium iminophenolate betaines have been prepared by a new synthetic procedure, and compared to their phosphonium counterparts. All of the betaines studied display negative solvatochromism as the solvent polarity increases and their absorption maxima are linearly related with the standard E J values for the Reichardt betaine dye, which suggests a possible application of these betaines as indicators of solvent polarity. A new family of triphenylphosphonium salts employing different donor groups has been synthesised and converted into related phosphine oxides. The compounds were found not to be greatly solvatochromic. Attempts to synthesise a range of “3-D” multi-chromophoric iminophenolate betaines have been carried out. However, at the present time the level of chromophore substitution is unknown, and the insolubility of the precursor salts has made isolation of the betaines very difficult. In situ formation of the betaines in the UV cell in a few solvents has shown the systems to be solvatochromic. A quinolinium iminophenolate betaine has been covalently attached to a soluble polystyrene support. An LB film of the polymer bound betaine was formed at Cranfield University; however subsequent Surface Plasmon Resonance (SPR) studies were unsuccessful. ACKNOWLEDGEMENTS Firstly I would like to thank my supervisor Professor David Allen for his help and guidance over the last three years; Steve, Donna and Sara for making my time in the lab “most enjoyable”; and the technical staff in the Division of Chemistry, especially Kev. Thank you to John, Chris and Donna (again) for the many memorable times at home, and of course to Matt for putting up with me whilst writing my thesis. Finally, I would like to thank my family for all their support over the last seven years. CONTENTS CHAPTER 1 Introduction 1.0 Introduction ...................................................................... ....................... 1 1.1 Solvent Polarity ........................................................................................ 1 1.2 Solvatochromism..................................................................................... 2 1.3 Empirical Scales of Solvent Polarity ................. ..................................... 4 1.4 Solvatochromic Compounds .................................................................. 11 1.5 Applications of Reichardt’s Betaine Dye .............................................. 17 1.6 Thermochromism, Piezochromism, Halochromism .............................. 18 1.7 Non-linear Optics .................................................................................... 19 1.8 Langmuir Blodgett Films ....................................................................... 24 1.9 Compounds Exhibiting NLO Properties ............................................... 28 1.10 Surface Plasmon Resonance ................................................................... 35 1.11 Aims of the Present Work ......................................... 36 References ............................................................................................... 40 CHAPTER 2 The Synthesis and the Characterisation of Phosphonium and Quinolinium Betaine Systems 2.0 Introduction ............................................................................................ 47 2.1 Long chain phosphoniophenyl imidazolide betaines ........................... 51 2.1.1 Synthesis of the imidazoles ................................................................... 51 2.1.2 Synthesis of N-hexadecyldiphenylphosphine....................................... 53 2.1.3 Synthesis of the long chain phosphonium salts ................................... 54 2.1.4 Synthesis of the long chain phosphonium betaines ............................. 56 2.1.5 Characterisation of the long chain salts and betaines .......................... 56 2.1.6 Solvatochromism studies ....................................................................... 57 2.1.7 Isotherm data ......................................................................................... 63 2.2 Long chain phosphonium benzylidene iminophenolate betaines 65 2.2.1 Synthesis of the imines ......................................................................... 65 2.2.2 Synthesis of the long chain phosphonium salts .................................. 66 2.2.3 Synthesis of the long chain phosphonium betaines ............................ 70 2.2.4 Characterisation of the starting materials, salts and betaines ............. 71 2.2.5 Solvatochromism studies of the long chain phosphonium betaines... 73 2.2.6 Micelle formation studies ......................................... 80 2.2.7 Isotherm data ......................................................................................... 83 2.3 Effects of annelation on the absorption properties of 4-(N- hexadecylpyridinium-4-ylmethylideneamino)-2,6-dihalophenolate systems ................................................................................................... 84 2.3.1 Synthesis of the quinoline imines ......................................................... 84 2.3.2 Synthesis of the betaines ........................................................................ 84 2.3.3 Characterisation of the quinolinium systems ...................................... 87 2.3.4 Solvatochromism studies ...................................................................... 87 2.3.5 Isotherm data ......................................................................................... 94 2.4 Effects of annelation on N-[-triphenylphosphoniobenzylidene]-4- amino-2,6-dichlorophenolate ................................................................. 97 2.4.1 Synthesis of 2-bromonaphthaldehyde ................................................. 97 2.4.2 Synthesis of the salt ..................................................................... 99 2.4.3 Synthesis of the betaine ........................................................................ 99 2.4.4 Characterisation of the naphthyl system .............................................. 100 2.4.5 Solvatochromism studies ...................................................................... 101 2.5 Effects of annelation on phosphonio-imidazolide
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