LAUSR

Abstract Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•− results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy•−)(CO)3X and Re(I)(bpy•−)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy•−)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.