Design, synthesis and characterisation of advanced switchable functional materials

Abstract

This thesis is part of an EPSRC-supported Metastable Materials project which focuses on designing new classes of solid-state advanced switchable materials. This thesis represents an important addition to exploring structure-property relations in the design, characterisation and analysis of switchable functional materials within the extent of coordination polymers (CPs).

The properties, synthesis and design of CPs are introduced in Chapter 1. Recently published developments and applications for switchable CPs are also introduced. The aims and objectives of this thesis are included.

The effects of reaction conditions and components upon lead-based CP architecture is studied in Chapter 2. 5-Ethynyl- and 5-allenyl- functionalised 1,3-benzenedicarboxylate linkers (ebdc and abdc) are reacted with Pb(OAc)·3H2O, and the effect of weak intermolecular interactions on CP packing and behaviour is discussed. Two single crystal to single-crystal (SCSC) transitions and one metallogel are observed and characterised.

Within Chapter 3, linkers ebdc and abdc were reacted with a series of first-row transition metal salts under varying conditions from which six structures in total were obtained and characterised. The extent of the effects of intermolecular interactions on resulting CP architecture is discussed, drawing on comparisons between the allenyl abdc and ethynyl ebdc functional groups.

In Chapter 4 the synthesis and characterisation of ten new frameworks comprising 4-(phenylethynyl)pyridine and a range of silver(I) salts are compared. The effects of intermolecular interactions on the resulting structures are discussed. Two structures were found to exhibit SCSC transitions on desolvation and heating, and the latter transition has been explored through DFT.

Chapter 5 details two cascade gas-induced reactions of a 1,8 bis(phenylethynyl)naphthalene guest loaded crystalline molecular flask [(ZnI2)3(tpt)2] (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine). A combination of crystallographic, gravimetric and spectroscopic techniques confirm the products and yields of both reactions.

Date of Award	23 Aug 2017
Original language	English
Awarding Institution	University of Bath
Supervisor	Charles Wilson (Supervisor), Andy Burrows (Supervisor) & Paul Raithby (Supervisor)