Bioinspired Photoactive Cu–Halide Coordination Polymers for Reduction Activation and Oxygen Conversion

Natural copper oxygenases provide fundamental principles for catalytic oxidation with kinetically inert molecular oxygen, but it remains a marked challenge to mimic both their structure and function in an entity. Inspired by the CuA enzymatic sites, herein we report two new photoactive binuclear copper–iodine- and bisbenzimidazole-comodified coordination polymers to reproduce the natural oxo-functionalization repertoire in a unique photocatalytic pathway. Under light irradiation, the Cu–halide coordination polymers effectively reduce NHP esters and complete oxygen reduction activation via photoinduced electron transfer for the aerobic oxidative coupling of hydroquinone with terminal alkynes, affording hydroxyl-functionalized ketones with high efficiency and selectivity. This supramolecular approach to developing bioinspired artificial oxygenases that merge transition metal- and photocatalysis supplies a new way to fabricate distinctive photocatalysts with desirable catalytic performances and controllable precise active sites.