Discrete Hexa- and Binuclear Heterometallic Iodobismuthate(III) Complexes with Cu(I) and Ag(I).

The rare examples of discrete anionic halobismuthates(III) with group 11 elements were obtained. Those are (3-MePyH)[BiCuI] () and (3,5-MePyC)[BiAgI] () (3-MePyH = 3-methylpyridinium cation, 3,5-MePyC=1,6-bis(3,5-dimethylpyridinium)hexane dication). Both complexes were isolated as pure phases; the optical band gaps for and are 1.

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](I)} () and (Py(CH)Py){[BiCl](I)} (), 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.

Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties.

Seven heterometallic iodoantimonates with the general formula (Cat){[SbMI]} (M = Cu(I) (1-6), Ag(I) (7)) were prepared. X-ray diffraction data indicate that these compounds are the first Sb(III) representatives of the structural type previously known only for heterometallic iodobismuthates(III). In 3 and 4, halogen-substituted cations form halogen bonds with the heterometallic halometalate chain.

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior.

Nine heterometallic iodobismuthates with the general formula Cat{[BiMI}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {BiI} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C.

Bismuth and antimony halometalates containing photoswitchable ruthenium nitrosyl complexes.

The first examples of Bi(III) and Sb(III) halide compounds combined with a photoswitchable ruthenium nitrosyl unit are reported. The structures of [RuNOPyBr][SbBr][SbBr] (1) and (HO)[RuNOPyBr][BiBr]·3HO (2) were determined by X-ray diffraction, and exhibit three different structural types of group 15 halometalates. Low-temperature IR-spectroscopy measurements reveal that the irradiation of 1 at 365 nm switches a stable Ru-NO (GS) unit to a metastable Ru-ON (MS1) linkage.