Stephen Brown (@niobiumalkoxide.bsky.social)

Photoinitiated Single-Crystal to Single-Crystal Redox Transformations of Titanium-Oxo Clusters Titanium-oxo clusters can undergo photochemical reactions under UV light, resulting in the reduction of the titanium-oxo core and oxidation of surface ligands. This is an important step in photocatalytic processes in light-absorbing Ti/O-based clusters, metal–organic frameworks, and (nano)material surfaces; however, studying the direct outcome of this photochemical process is challenging due to the fragility of the immediate photoproducts. In this report, titanium-oxo clusters [TiO(OiPr)(L)]n (n = 4, L = O2PPh2, or n = 6, L = O2CCH2tBu) undergo a two-electron photoredox reaction in the single-crystal state via an irreversible single-crystal to single-crystal (SC-SC) transformation initiated by a UV laser. The process is monitored by single crystal X-ray diffraction revealing the photoreduction of the cluster with coproduction of an (oxidized) acetone ligand, which is retained in the structure as a ligand to Ti(3+). The results demonstrate that photochemistry of inorganic molecules can be studied in the single crystal phase, allowing characterization of photoproducts which are unstable in the solution phase. https://pubs.acs.org/doi/10.1021/jacs.4c04068