Thiatruxene-Based Conductive\nMOF: Harnessing Sulfur\nChemistry for Enhanced Proton Transport

Functionalizing the organic building blocks of electrically\nconductive\nMOFs (EC-MOFs) can be a powerful method for adjusting the electronic\nstructure and introducing a specific chemistry. However, designing\nEC-MOF linkers with reactive functional groups for postsynthetic modification\nis challenging due to the requirements of d-p conjugation. This work\naddresses such design limitations by synthesizing an EC-MOF, Cu-thiatruxene\n(Cu-thiaTRX). This conductive framework incorporated a truxene-based\nlinker with heterocyclic sulfur, allowing for efficient conjugation\nand an electrical conductivity of 2.2 × 10<sup>–2</sup> S cm<sup>–1</sup>. Harnessing sulfur chemistry in Cu-thiaTRX\ninvolves a two-step postsynthetic modification: oxidation and S<sub>N</sub>Ar. The sulfinic groups introduced in the framework enabled\ntunable proton conductivity, leading to a 200-fold improvement. These\nresults highlight the importance of a rational linker design for functionalization.