Electronic structures and binding properties of chalcogenolate-bridged molecular wheels of ruthenium and osmium

Abstract

We present here a Density Functional Theory (DFT) study on the electronic structures and binding properties of chalcogenolate-bridged molecular wheels of ruthenium and osmium [M(ER)2(CO)2]n (M = Ru or Os, E = S or Se, R = alkyl or aryl group, and n = 6 or 8). Both the electronic structures and absorption properties of [M(ER)2(CO)2]n wheels are only slightly perturbed by the metal ion and the organochalcogenolate ligand. Replacement of CO by pyridine reduces the HOMO–LUMO energy gap from 2.68 eV to 1.01 eV based on PBE/def2-SVP calculations. The binding properties of [M(ER)2(CO)2]n towards small molecules and alkali metal ions have also been examined by DFT calculations.