Exploring the Photophysics and Photocatalytic Activity of Heteroleptic Rh(III) Transition-Metal Complexes Using High-Throughput Experimentation.

High-throughput synthesis and screening (HTSS) methods were used to investigate the photophysical properties of 576 heteroleptic Rh(III) transition-metal complexes through measurement of the UV-visible absorption spectra, deaerated excited-state lifetime, and phosphorescent emission spectra. While 4d transition-metal photophysics are often highly influenced by deleterious metal-centered deactivation channels, the HTSS of structurally diverse cyclometalating and ancillary ligands attached to the metal center facilitated the discovery of photoactive complexes exhibiting long-lived charge-transfer phosphorescence (0.15-0.95 μs) spanning a substantial portion of the visible region (546-620 nm) at room temperature. Further photophysical and electrochemical investigations were then carried out on select complexes with favorable photophysics to understand the underlying features controlling these superior properties. Heteroleptic Ir(III) complexes with identical ligand morphology were also synthesized to compare these features to this family of well understood chromophores. A number of these Rh(III) complexes contained the requisite properties for photocatalytic activity and were consequently tested as photocatalysts (PCs) in a water reduction system using a Pd water reduction cocatalyst. Under certain conditions, the activity of the Rh(III) PC actually surpassed that of the Ir(III) PC, uncovering the potential of this often-overlooked class of transition metals as both efficient photoactive chromophores and PCs.