Direct Observation of a {Re6(μ3-S)8} Core-to-Ligand Charge-Transfer Excited State in an Octahedral Hexarhenium Complex

A new complex, [Re6S8Cl5PPY](3-) (PPY = 4-phenylpyridine), was synthesized and characterized. The complex showed red emission at 296 K in both the crystalline phase and CH3CN. The transient absorption spectrum of [Re6S8ClsPPY](3-) revealed that the emissive excited state involved the {Re-6(mu(3)-S)(8)} core-to-ligand charge-transfer character.