MLCT excited states of cuprous bis-phenanthroline coordination compounds

Abstract

Cuprous bis-phenanthroline compounds possess metal-to-ligand charge transfer, MLCT, excited states. Phenanthroline ligands coordinated to Cu(I) that are disubstituted in the 2- and 9-positions with alkyl or aryl groups, abbreviated CuI(phen′)2+, have long-lived excited states at room temperature. The parent CuI(phen)2+ compound is non-emissive under the same conditions with a short excited state lifetime, τ<10 ns. Disubstitution in the 2,9-positions stabilizes the Cu(I) state and increases the energy gap between the MLCT and the ground state. The prototypical and most well studied compound is CuI(dmp)2+, where dmp is 2,9-(CH3)2-1,10-phenanthroline. In dichloromethane solution at room temperature, CuI(dmp)2+ displays broad MLCT absorption with λmax=454 nm, a broad unstructured emission with λmax=730 nm, and an excited state lifetime of 85 ns. The emission arises from two closely spaced MLCT excited states, separated in energy by 1800 cm−1, that behave as one state at room temperature. CuI(dmp)2+* excited states are quenched in the presence of Lewis bases and coordinating solvents. A 5-coordinate excited state complex, or exciplex, is proposed to account for temperature dependent quenching data. The substantial inner-sphere reorganizational energy changes that follow light excitation are novel features of these MLCT excited states. This review attempts to cover all the existing data reported on CuI(phen′)2+ excited states and contrast it with well-known MLCT behavior of (dπ)6 transition metal compounds.