Preparation, photoluminescence and excited state properties of the homoleptic cluster cation [(W6I8)(CH3CN)6]4+

Abstract

Solvated tungsten iodide cluster compounds are presented with the homoleptic cluster cation [(W₆I₈)(CH₃CN)₆]⁴⁺ and the heteroleptic [(W₆I₈)I(CH₃CN)₅]³⁺, synthesized from W₆I₂₂ in acetonitrile. Crystal structures were solved and refined on deep red single-crystals of [(W₆I₈)(CH₃CN)₆](I₃)(BF₄)₃·H₂O, [(W₆I₈)I(CH₃CN)₅](I₃)₂(BF₄), and on a yellow single-crystal of [W₆I₈(CH₃CN)₆](BF₄)₄·2(CH₃CN) on the basis of X-ray diffraction data. The structure of the homoleptic [(W₆I₈)(CH₃CN)₆]⁴⁺ cluster is based on the octahedral [W₆I₈]⁴⁺ tungsten iodide cluster core, coordinated by six apical acetonitrile ligands. The electron localisation function of [(W₆I₈)(CH₃CN)₆]⁴⁺ is calculated and solid-state photoluminescence and its temperature depedence are reported. Additionally, photoluminescence and transient absorption measurements in acetonitrile are shown. Results of the obtained data are compared to compounds containing [(M₆I₈)I₆]²⁻ and [(M₆I₈)L₆]²⁻ (M = Mo or W; L = ligand) clusters.