TY - JOUR

T1 - Iodine-Rich Supramolecular Complexes of Chlorobismuthates(III): Unusual Lone Pair Activity and Features of Halogen Bonding in Crystals

AU - Korobeynikov, Nikita A.

AU - Usoltsev, Andrey N.

AU - Sokolov, Maxim N.

AU - Novikov, Alexander S.

AU - Adonin, Sergey A.

PY - 2024/9/9

Y1 - 2024/9/9

N2 - The first chrorobismuthate(III) supramolecular hybrids with halogen-bond-linked I2, (Py(CH2)2Py){[BiCl5](I2)} (1) and (Py(CH2)3Py){[BiCl5](I2)0.5} (2), were synthesized via the reaction between Bi2O3, I2, 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 1, Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I2 pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.

AB - The first chrorobismuthate(III) supramolecular hybrids with halogen-bond-linked I2, (Py(CH2)2Py){[BiCl5](I2)} (1) and (Py(CH2)3Py){[BiCl5](I2)0.5} (2), were synthesized via the reaction between Bi2O3, I2, 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 1, Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I2 pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.

UR - https://www.mendeley.com/catalogue/8bb2fd9c-4d42-3564-8271-587e3d751020/

U2 - 10.1021/acs.inorgchem.4c02593

DO - 10.1021/acs.inorgchem.4c02593

M3 - Article

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -