A Novel Family of Polyiodo‐Bromoantimonate(III) Complexes: Cation‐Driven Self‐Assembly of Photoconductive Metal‐Polyhalide Frameworks

: In the presence of different cations, reactions of [SbBr6 ]3- and I2 result in a new family of diverse supramolecular 1D polyiodide-bromoantimonate networks. The coordination number of Sb, as well as geometry of assembling {Ix }n- polyhalide units, can vary, resulting in unprecedented structural types. The nature of I⋅⋅⋅Br interactions was studied by DFT calculations; estimated energy values are 1.6-6.9 kcal mol-1 . Some of the compounds showed strong photoconductivity in thin films, suggesting multiple feasible applications in optoelectronics and solar energy conversion.