ew sul ide-apped octahedral he aihenium (III) complexes containing 4-phenylpyridine (ppy) or 1,2-bis(4-pyr-idylethane (bpe) ((n-C-4 (9))(4)N)[mer-{Re6S8Cl3(ppy)(3) Bu-4)[1]), ((n-C-4 (9))(4)N)(2) trans-{Re6S8Cl4(bpe)(2) Bu-4 )(2)3a]), and ((n-C-4 (9))(4)N)(2) cis-{Re6S8Cl4(bpe)(2) Bu-4 )(2) 3b]} were prepared, and X-ray single-crystal structure determination way carried Out or (Bu-4 )(2) 2a] and (Bu-4 )(2) 3a]. The photophysical properties of these comple es were studied both in acetonitrile at and in the solid state at and along with those a the known '-bipyridine (Bpy) analogues ((n-C-4 (9))(4)N)[mer-{Re6S8Cl3(bpy)(3) Bu-4 )[4]), {(n-C-4 (9))4(N))(2-)[trans-{Re6S8Cl4(bpy)(2) Bu-4 )(2) 5a]), and ((n-C-4 9)(4) cis-{Re6S8Cl4(bpy)(2) Bu-4 )(2) 5b]}. The photophysical data o [5a](2-) and [5b](2-) in solution and in the solid state were significantly different from those of other comple es On the basic o e perimental observations o [2a]2- and [5a]2- and density-functional theory (DFT) calculations, it was concluded that [5]2- and [5b]2- in solution and in the solid state were significantly different from those of other comple es On the basic o e perimental observations o [2a]2- and [5a]2- and density-functional theory (DFT) calculations, it was concluded that [5a]2- and [5b]2- in solution and in the solid state were significantly different from those of other comple es On the basic a e perimental observations o [2a]2- and [5a]2- and density-functional theory (DFT) calculatins, it was concluded that [5a]2- and [5b](2-) exhibited metal (Re6S8 core)-to-ligand (bpy) charge transfer (MLCT) type emission. This is the first unambiguous demonstration of MLCT type emissions for the hexarhenuim comple es he MC components, whrer present, are only minor in the case o the emissions o [1](-), [2a](2-), [2b](2-), and [4](-); these can be explained primarily as the contributions of the intracore electronic transitions. The emissions o [3a](2-) and [3b](2-) can be assigned almost completely to the electronic transitions within the Re6S8 core he dierent emission characteristics of the bis(bpy) complexes ([5a](2-) and [5b](2-) from the tris(bpy) complex ([4](-) are a results of the increase in the number of nitrogen donors on the Re6S8 core, which stabilities the Re6S8 core energy to a lower level than the energy of the bpy ligand pi orbital On the other hand, it has been shown that the emissions of the bis(PPy) level than the energy of the bpy ligand pi orbital On the other ahnd, it has been shown that the emissions of the bis(ppy) 2a](2-) and [2b](2-) and bis(bpe) complexes ([3a](2-) and [3b](2-) are best characterized bu the higher pi enerty level to each heteroaromatic ligand, which lead to a stronger metal character in the emissive e cited state of the complx