Iodine-Rich Supramolecular Complexes of Chlorobismuthates(III): Unusual Lone Pair Activity and Features of Halogen Bonding in Crystals.

The first chrorobismuthate(III) supramolecular hybrids with halogen-bond-linked I, (Py(CH)Py){BiCl} () and (Py(CH)Py){BiCl} (), were synthesized via the reaction between BiO, I, and salts of the corresponding cations in HCl. The compounds featured one- and two-dimensional (2D) supramolecular motifs built by I···Cl contacts; in the case of , Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.