Development of Redox-Active Metal-Organic Frameworks for Applications in Porous Conductors

Abstract

This thesis details the electrochemical, spectroscopic and structural characterisation of several families of redox-active coordination frameworks using PXRD, UV-Vis-NIR, IR, Raman and EPR spectroscopies, as well as DC cyclic voltammetry and large amplitude AC voltammetry. A significant emphasis was placed on the development of in situ solid-state UV-Vis-NIR and Raman spectroelectrochemistry (SEC) measurements which were used to test the properties of electroactive frameworks and gain an insight into the mechanism of redox transformations. From these experiments, the current generation of the solid-state SEC cells were critically assessed and the necessary modifications for the future designs highlighted. Furthermore, various aspects of charge transfer complex formation and their properties inside frameworks were investigated using a combination of spectroscopic and electrochemical techniques. These investigations provided deeper insights into the nature of electron transfer in electroactive coordination frameworks which paves the way towards elucidating structure-property relationships. Understanding the parameters governing the redox behaviour is essential for the design of frameworks with desired properties.