Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis.

A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around a metal's coordination sphere. As a model system, gold(I) complexes of these NHCs exhibit efficient bidirectional E - Z isomerization under visible light, offering a versatile platform for reversibly photomodulating the reactivity of organogold species. Comprehensive kinetic studies of the protodeauration reaction reveal rate differences of up to 2 orders of magnitude between the E and Z isomers of the NHCs, resulting in a quasi-complete visible-light-gated ON/OFF switchable system. Such a high level of photomodulation efficiency is unprecedented for gold complexes, challenging the current state-of-the-art in photoswitchable organometallics. Thorough investigations into the ligand properties paired with structure-reactivity correlations underscored the unique ligand's steric features as a key factor for reactivity. This effective photocontrol strategy was further validated in gold(I) catalysis, enabling in situ photoswitching of catalytic activity in the intramolecular hydroalkoxylation and -amination of alkynes. Given the significance of these findings and its potential as a widely applicable, easily customizable photoswitchable ancillary ligand platform, azImBA is poised to stimulate the development of adaptive, multifunctional metal complexes.