Structure–Property Engineering of Redox‐Active Tetrathiafulvalene‐ and Bipyridine‐Based Metal–Organic Frameworks for Battery Cathodes

Redox‐active metal–organic frameworks (MOFs) are gaining increasing attention as next‐generation electrode materials owing to their tuneable porosity, structural versatility, and ability to host electronically active ligands. Tetrathiafulvalene (TTF) derivatives are an attractive class of π‐conjugated redox units for constructing MOFs that exhibit efficient charge transport. In this study, we investigated the structure–property relationships of TTF‐based MOFs by employing tetrathiafulvalene‐tetrabenzoate (H 4 TTFTB) as a multi‐electron redox ligand. We first investigated Cd 2 (TTFTB) MOF, a representative TTF‐MOF with relatively high electronic conductivity, as a cathode material for lithium‐ion and sodium‐ion batteries. Cd 2 (TTFTB) MOF delivers stable cycling and competitive rate capability, particularly in sodium‐ion systems, benefiting from its robust framework and intrinsic porosity, which facilitate ion diffusion. To further enhance the charge‐storage performance, we introduced bipyridine co‐ligands to construct TTF‐hybrid‐MOF with dual redox centers. The resulting framework exhibits a markedly improved capacity and electronic conductivity through synergistic redox activity. This study demonstrates a molecular‐level design strategy for activating multielectron redox centers in conductive MOFs, highlighting TTF‐based coordination frameworks as versatile and promising cathodes for rechargeable batteries.