Optical property trends in a family of {Mo6I8} aquahydroxo complexes

Abstract

Luminescence is one of the key properties of octahedral molybdenum cluster complexes and the basis for most areas of their possible practical applications. Nevertheless, the factors affecting the optical properties of the clusters are insufficiently studied and establishing them will allow us to tune both absorption and emission more precisely. In this work, we obtained two new cationic [{Mo₆I₈}(H₂O)₄(OH)₂](An)₂·nH₂O (An = NO₃⁻, n = 3; An = OTs⁻, n = 2, OTs⁻ – p-toluenesulfonate), and two neutral [{Mo₆I₈}(H₂O)₂(OH)₄]·nH₂O (n = 2, 12) aquahydroxo complexes. Due to the similar compositions of the clusters obtained, we determined the influence of crystal packing and ligand environment on the absorption and photo- and radioluminescence properties. Thus, the four-component nature of the cluster emission was established using Gaussian deconvolution of the photoluminescence spectra. It was shown that the influence of both ligand type and crystal density decreases when moving to the red (lower-energy) part of the spectra, with only the first two components located in the blue (higher-energy) part of the spectra being strongly affected. Also, it was found that protonation of two hydroxo ligands leads to a significant decrease in absorption in the visible spectral region.