The Remarkably Robust, Photoactive Tungsten Iodide Cluster [W6I12(NCC6H5)2]

Abstract

AbstractThe new heteroleptic tungsten iodide cluster compound [W6I12(NCC6H5)2] is presented. The synthesis is carried‐out from Cs2W6I14 and ZnI2 under solvothermal conditions in benzonitrile solution, yielding red cube‐shaped crystals. [W6I12(NCC6H5)2] represents a heteroleptic [W6I8]‐type cluster bearing four apical iodides and two benzonitrile ligands. Molecular [W6I12(NCC6H5)2] clusters form a robust hydrogen bridged crystal structure with high thermal stability and high resistibility against hydrolysis. The electronic structure is analyzed by quantum chemical methods of the calculated electron localization function (ELF) and the band structure. Photoluminescence measurements are performed to verify and describe the photophysical properties of [W6I12(NCC6H5)2]. Finally, the photocatalytic properties of [W6I12(NCC6H5)2] are evaluated as a proof‐of‐concept.