CONDUCTIVE M–PYRAZOLATE COORDINATION FRAMEWORKS BASED ON REDOX-ACTIVE AROMATIC DIIMIDES

The effectiveness of a solid-state material as a semiconducting entity within contemporary electronic frameworks fundamentally hinges on its molecular structure. Chapter 1 provides a foundational elucidation of charge transport within ordered solids, delineating the through-space and through-bond charge transport pathways within supramolecular assemblies. However, the deliberate manipulation of such charge transport routes to attain heightened conductivity levels poses a significant challenge. Therefore, strategies involving hydrogen bonding and metal coordination to orchestrate the assembly of supramolecular structures, with the aim of achieving pronounced π-orbital overlap within each corresponding charge transport pathway are introduced. Chapter 2 explores harnessing hydrogen bonding to autonomously assemble monomeric units in the solid state, surmounting the inherent repulsion between aromatic π-surfaces and culminating in the creation of organic material proficient in through-space charge transport through the convergence of discrete π-orbitals. Chapter 3, building upon the material obtained in Chapter 2, centres on the development of a coordination polymer possessing robust chemical and thermal characteristics. The objective is to propagate both through-bond and through-space charge transport pathways, thereby yielding highly conductive materials tailored for energy storage applications. In Chapter 4, an isoreticular strategy was implemented to scrutinise the manipulation of the topological framework of the material acquired in Chapter 3. To generate isostructural materials endowed with augmented charge transport pathways, Fe-salts containing anions of different sizes were used, leading to frameworks with identical topologies. In Chapter 5, the selection of an alternative inorganic linker to what was observed in Chapters 3 and 4 will be examined to discern the impact of distinctive coordination modes on charge transport pathways. While the methodologies for modulating the through-space and through-bond pathways are currently undergoing refinement, this Thesis endeavours to underscore the efficacy of deploying hydrogen bonding and isoreticular design strategies in shaping molecular assemblies towards achieving elevated levels of conductivity.