Photoactivated CO-releasing molecules (photoCORMs) are potential therapeutics for internal delivery of the gasotransmitter CO. In this work, we extend a previously described strategy of leveraging the metal-metal-to-ligand charge transfer (MMLCT) optical transition to release CO from heterobimetallic carbonyls with the general formula [(CO)5MnRe(CO)3(L)]. (L = 2,2’-bipyridine, 1,10-phenanthroline, 2,2’-biquinoline, 1,10-phenanthroline-5-carboxaldehyde, and 1,10-phenanthroline-5-carboxylic acid). Heterocyclic bidentate ligand L, coordinated to rhenium tricarbonyl moiety, imparts an emissive property alongside the molecules’ CO-releasing tendency at longer wavelengths (~600 nm). Photolysis of [(CO)5MnRe(CO)3(L)] with green light leads to homolytic cleavage of the Re-Mn bond to form reactive metal oxide species, which decompose to yield CO. The effect of varying ligands on photochemical activity of [(CO)5MnRe(CO)3(L)] is investigated.

Long wavelength light-induced CO release and luminescence from a series of heterobimetallic photoCORMs

ACS Spring 2022

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