Control of the Hydroquinone/Benzoquinone Redox State in High‐Mobility Semiconducting Conjugated Coordination Polymers

Conjugated coordination polymers (c‐CPs) are unique organic–inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c‐CPs while maintaining the structural topology. The redox‐state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5‐tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag 4 TTHQ and Ag 4 TTBQ (TTBQ=1,2,4,5‐tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two‐dimensional Ag−S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag 4 TTHQ and 0.5 eV for Ag 4 TTBQ) and conductivities (0.4 S/cm for Ag 4 TTHQ and 10 S/cm for Ag 4 TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag 4 TTHQ. Consequently, Ag 4 TTHQ displays a high Seebeck coefficient of 330 μV/K and a power factor of 10 μW/m ⋅ K 2 , surpassing Ag 4 TTBQ and the other reported silver‐based c‐CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm 2 /V ⋅ s in both Ag 4 TTHQ and Ag 4 TTBQ.