Direct observation of a {Re6(μ3-S)8} core-to-ligand charge-transfer excited state in an octahedral hexarhenium complex.

A new complex, [Re(6)S(8)Cl(5)ppy](3-) (ppy = 4-phenylpyridine), was synthesized and characterized. The complex showed red emission at 296 K in both the crystalline phase and CH(3)CN. The transient absorption spectrum of [Re(6)S(8)Cl(5)ppy](3-) revealed that the emissive excited state involved the {Re(6)(μ(3)-S)(8)} core-to-ligand charge-transfer character.