Tailoring Redox Activity in Metal-Organic Frameworks (MOFs) to Unlock Emergent Electronic Behaviours

This thesis reports an investigation into redox-active metal-organic frameworks (MOFs) from design principles through to structural, electrochemical, and spectroscopic insights into their unique electronic behaviours. The interactions between electroactive ligand components, such as through-space ligand-to-ligand charge transfer (CT) and π-π interactions, were explored and exploited as a platform for conductive and chemi-responsive materials. Additionally, the use of both de novo and post-synthetic modification design strategies were explored to examine the modularity of MOFs. The redox and spectroscopic properties of these materials were probed using a range of techniques including single crystal X-ray diffraction (SCXRD), UV-vis-NIR and Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy, conductivity, in addition to vis-NIR and EPR spectroelectrochemistry (SEC) to elucidate structure—property relationships. This work demonstrates the enormous potential of redox-active MOFs as multifunctional materials based on their tunable properties as a function of redox state. As such, the fundamental investigations presented here pave the way towards a more targeted approach to tunable electroactive solid state materials.