Mixed Ionic and Electronic Conductivity in a Tetrathiafulvalene-Phosphonate Metal–Organic Framework

Abstract

Mixed ionic-electronic conductors have great potential as materials for energy storage applications. However, despite their promising properties, only a handful of metal–organic frameworks (MOFs) provide efficient pathways for both ion and electron transport. This work reports a proton–electron dual-conductive MOF based on tetrathiafulvalene(TTF)-phosphonate linkers and lanthanum ions. The formation of regular, partially oxidized TTF stacks with short S···S interactions facilitates electron transport via a hopping mechanism, reporting a room-temperature conductivity of 7.2 × 10^–6 S cm^–1. Additionally, the material exhibits a proton conductivity of 4.9 × 10^–5 S cm^–1 at 95% relative humidity conditions due to the presence of free −POH groups, enabling efficient proton transport pathways. These results demonstrate the potential of integrating electroactive building blocks along with phosphonate groups toward the development of mixed ionic-electronic conductors.