A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior

Inorg Chem. 2023 Feb 27;62(8):3485-3497. doi: 10.1021/acs.inorgchem.2c03785. Epub 2023 Feb 13.

Abstract

Photoinduced electricity and proton conductivity led fuel cells have emerged, inter alia, as highly promising systems for unconventional energy harvesting. Notwithstanding their individual presence with widely acclaimed results, an integrating system with mutually inclusive manifestation of both features has hitherto not been reported in the literature. To achieve this objective, our approach was to design a ligand system incorporating prerequisite features of both systems, like extended conjugation instigating photophysical activity and functional groups facilitating ionic conduction. As such, we report herein the design, synthesis, and characterization of a pyridyl-pyrazole-based silver compound that exhibits an excellent photocurrent generation and very high proton conductivity. The X-ray single-crystal structure of the Ag complex fully supports our notion, showing extensive π-π conjugated aromatic rings with a protruding free sulfonic group, facing toward solvent-filled channels with numerous supramolecular interactions. The nanoscopic silver metallogel induces semiconductive features in the system which ultimately result in photoresponse behavior in terms of photocurrent generation with an whopping photocurrent gain (Ion/Ioff) of 21.2. To complete the idea of an integrated system, the proton conductivity values were also measured for both gel and crystalline states, while the former state yields a better result. The maximum proton conductivity value turns out to be 1.03 × 10-2 S cm-1 at 70 °C, which is higher than or comparable to those of well-known systems in the literature for proton conductivity.