Near-Infrared And Visible Photoactivation To Uncage Carbon Monoxide From An Aqueous-Soluble Photocorm

Multiphoton excitation allows one to access high energy excited states and perform valuable tasks in biological systems using tissue penetrating near-infrared (NIR) light. Here, we describe new photoactive manganese tricarbonyl complexes incorporating the ligand 4'-p-N,N-bis(2-hydroxyethyl)amino-benzyl-2,2':6',2 ''-terpyridine (TPYOH), which can serve as an antenna for two photon NIR excitation. Solutions of Mn(CO)(3)(TPYOH)X (X = Br- or CF3SO3-) complexes are very photoactive toward CO release under visible light excitation (405 nm, 451 nm). The same responses were also triggered by multiphoton excitation at 750 and 800 nm. In this context, we discuss the potential applications of these complexes as visible/NIR light photoactivated carbon monoxide releasing moieties (photoCORMs). We also report the isolation and crystal structures of the TPYOH complexes Mn(TPYOH)Cl-2 and [Mn(TPYOH)(2)](CF3SO3)(2), to illustrate a possible photolysis product(s).