This project is concerned with achieving visible/near-infrared light activated carbon monoxide release at physiological targets. Early photoCORMs (photo-activated carbon monoxide releasing moieties) typically release CO upon photo-excitation of ligand field (LF) states of metal carbonyl complexes. LF transitions are generally high energy in such complexes and require UV or short visible wavelengths for photolabilization. These wavelengths have the disadvantage of poor penetration into mammalian tissue and can cause detrimental effects to living cells. In this work, we synthesized a group of rhenium-manganese dinuclear metal carbonyl complexes of the type (CO)5ReMn(CO)3(L) (L = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2-biquinoline (biq) or 1,10-phenanthroline-4-carbaldehyde (phenCHO)) and (CO)5MnRe(CO)3(bpy). A new CO releasing mechanism is discovered in those complexes, where we utilize excitation of metal-metal bond to ligand (σMM -&gt; πL*) charge transfer (MMLCT) transition to homolytically cleave metal-metal bonds and generate reactive intermediates (proCORMs) that release CO upon subsequent reaction(s). Some of those complexes, different from our early work with photoCORMs incorporating upconverting nanoparticles, are able to absorb NIR light and proved to be photo-reactive under 794 nm laser irradiation. In this context, we are studying photochemistry of these dinuclear carbonyl complexes and their potential applications on physiological targets.

Dinuclear photoCORMS: Visible/near-infrared light activating CO release

253rd National Meeting (2017)

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