Extending the Chevrel-type superatoms to the nitrogen family

Abstract

Chevrel-type superatoms refer to the ligated transition metal chalcogenide clusters M₆E₈L₆, where the octahedral M₆ is face-capped with cubic chalcogen E₈ (E = S/Se/Te). Most transition metals can form such superatoms and many organic and inorganic ligands can be substituted in solution reactions, which allows these atomic precision species to be easily functionalized and their properties to be tunable. No test was reported for substituting the chalcogens with pnicogens in this class of materials. In this article, we try to discover if such substitutions are possible. Combining different transition metals and ligands, theoretical computations show that [M₆Q₈(CN)₆]²⁻ (Q = P, As, Sb) for M = Co, Rh, Ir, and Ni, Pd, Pt have closed electronic shells and possess enhanced thermal and chemical stabilities. Analyses of the electronic structures indicate high similarity between the M–M and M–Q/M–S interactions in these species.