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.