Coordination of apical O- and S-donor ligands to the hexarhenium(III) cluster core: Investigating the electrochemistry of alcoholate containing cluster complexes

[Display omitted] •Synthesis of rhenium selenide clusters with alcoholate and thiolate ligands.•Cyclic voltammograms of the alcoholate clusters reveal complex electrochemical behavior.•These clusters emit in the red-NIR region in solution.•X-ray structures of the methoxide, phenoxide and thiophenolate complexes are reported. The alkoxide containing rhenium selenide cluster, [Re6Se8(PEt3)5(OMe)]+, was synthesized from [Re6Se8(PEt3)5(py)]2+ and NaOMe. This methoxide complex was then used as a precursor in the preparation of two other site-differentiated species, the phenoxy [Re6Se8(PEt3)5(OPh)]+ and thiophenolate [Re6Se8(PEt3)5(SPh)]+ cluster complexes. The synthesis of the 4-methylbenzenethiolate complex, [Re6Se8(PEt3)5(STol)]+, prepared via a different synthetic route, is also reported along with the single crystal X-ray diffraction analyses of the methoxy, phenoxy and thiophenolate complexes. The electrochemistry of the alcoholate complexes reveals a multitude of redox processes; solutions of these complexes were also found to emit in the red-NIR region.