Abstract

The calculated relativistic molecular orbitals of the 23eRe6Q8X63- cluster ions indicate that the manifold of closely spaced unoccupied energy levels are mainly localized on the octahedral [Re6Q8]3+ core, while the cluster highest occupied molecular orbitals are largely centered on the terminal ligands. Thus, the electronic features of the excited states of the 23e clusters are quite similar with those of the intensely luminescent diamagnetic Re6Q8X64- 24e cluster ions. The calculated and observed spin-dependent parameters support the reassignment of these 23e clusters as the nonprotonated Re6Q8X63- species.