This thesis details the study of structure-property relationships in redox-active coordination frameworks. The structural tuneability of framework materials was used to create a series of inter-related, hierarchical frameworks. A combined spectroscopic, electrochemical, electronic and structural study was used to derive key parameters of redox-active frameworks towards the assessment of their degree of delocalisation – a key feature for their integration into application such as Field-Effect Transistor (FET) devices, energy storage, optoelectronics and many more. Despite the wealth of applied studies on redox-active frameworks, fundamental understandings of electron transfer within a framework manifold and the consequence of redox-modulation within a crystalline 3-D material is less understood.
The work herein describes a novel ‘hierarchical approach’ to elucidating the fundamental relationships that exist between the structural, electrochemical, spectroscopic and electronic properties applicable beyond electroactive frameworks. A perspective of previously reported redox-active frameworks is presented in Chapter 1. Chapters 2-5 explores two approaches, the ‘through-bond’ and ‘through-space’ approach, to induce long-ranged electronic delocalisation in coordination framework materials. A number of key physical properties such as redox state, conductivity and extent of delocalisation of these examples were characterised to build and recognise structure-property relationships. Understanding the nature of electron transfer in a framework manifold should pave the way towards designing materials with fine-tuned properties