Synthesis and Properties of Redox-Switchable Non-Linear Optically Active Polyoxometalate Chromophores

Hood, Bethany (2022) Synthesis and Properties of Redox-Switchable Non-Linear Optically Active Polyoxometalate Chromophores. Doctoral thesis, University of East Anglia.

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Abstract

This thesis discusses the synthesis and properties of a series of sterically protected redox-switchable non-linearly optically active polyoxometalate chromophores. A second series of compounds designed with the purpose of increasing non-linear optical activity over previously synthesised compounds is also discussed.

Chapter 1 gives an introduction into the background of Lindqvist polyoxometalates and their derivatives as well as non-linear optics and the NLO active chromophores synthesised over the years, while chapters 2 and 3 discuss the synthesis and analysis of nine sterically protective Lindqvist derivatives, five of which feature the amine electron donors needed for nonlinear optical activity. Two compounds featuring electron accepting nitro groups were also synthesised and investigated. The linear optical and electrochemical properties of the compounds are discussed in chapter 2 while chapter 3 explores the non-linear optical properties of the Lindqvist derivatives using DFT and Hyper-Rayleigh scattering, with the Hyper-Rayleigh experiments revealing redox-switchable responses observed for the first time in polyoxometalate chromophores.

The work discussed in chapter 4 focuses on two series of novel multi-dimensional polyoxometalate chromophores, with the synthesis and properties of both one-donor-two-acceptor and two-donor-one-acceptor derivatives being discussed. These compounds are investigated by UV-vis absorption spectrometry, cyclic voltammetry, and Hyper Rayleigh Scattering. In chapter 5, the synthesis and properties of the first polyoxometalate chromophore featuring an alkene bridge between the amine donor and the POM acceptor is discussed, as well as the attempted synthesis of a similar but sterically protected analogue. The compound, like those in previous chapters, are investigated by UV-vis spectroscopy, DFT, electrochemistry, and Hyper-Rayleigh scattering, to reveal high NLO activity.

Item Type:	Thesis (Doctoral)
Faculty \ School:	Faculty of Science > School of Chemistry
Depositing User:	Kitty Laine
Date Deposited:	05 Dec 2022 11:52
Last Modified:	05 Dec 2022 11:52
URI:	https://ueaeprints.uea.ac.uk/id/eprint/89986
DOI:

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