A recent area of interest for dimeric transition metal complexes has been their visible light photochemistry. As compared to monomeric complexes that have traditionally been used for such applications (e.g., the archetypal Ru(bpy)3Cl2 and its many analogues), it has been found that metal–metal interactions provide an additional handle for tuning photophysical properties such as absorption wavelength, excited state lifetime, and excited state redox potentials. Metal dimers have therefore begun to receive significant attention for applications in light harvesting, photo-induced electron transfer reactions, and photoredox catalysis. A drawback, however, is that the systems reported to date are generally based on expensive precious metal dimers such as rhodium or platinum. Unsurprisingly, silver has not previously been viewed as a promising candidate for applications in photochemistry with visible light. Silver(I) complexes, with d10 electronic configurations, are typically colorless, and higher oxidation state complexes of silver with partially filled d shells generally exhibit poor stability that precludes their use in such applications. Our group has recently discovered that dimeric silver(I) complexes with redox-active ligands can display unusual absorption features in the visible region, which arise from a combination of close silver–silver interactions and low-lying ligand π* orbitals. In this poster we describe our work on the synthesis and characterization of new silver(I) dimers for applications in visible light photochemistry, with a focus on how changes in the supporting ligand scaffold impact photophysical properties.

Visible light photochemistry with dinuclear silver(I) complexes

ACS Spring 2022

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