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<sub>2</sub>, (Py(CH<sub>2</sub>)<sub>2</sub>Py){[BiCl<sub>5</sub>](I<sub>2</sub>)} (<b>1</b>) and (Py(CH<sub>2</sub>)<sub>3</sub>Py){[BiCl<sub>5</sub>](I<sub>2</sub>)<sub>0.5</sub>} (<b>2</b>), were synthesized via the reaction between Bi<sub>2</sub>O<sub>3</sub>, I<sub>2</sub>, 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 <b>1</b>, Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I<sub>2</sub> pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.
Authors
- Maxim N. Sokolov⧫ (ORCID: https://orcid.org/0000-0001-9361-4594)
- Sergey A. Adonin (ORCID: https://orcid.org/0000-0002-9889-5273)
- Alexander S. Novikov (ORCID: https://orcid.org/0000-0001-9913-5324)
- Andrey N. Usoltsev (ORCID: https://orcid.org/0000-0003-3980-5028)
- Nikita A. Korobeynikov (ORCID: https://orcid.org/0000-0003-3399-5975)
Institutions
- Peoples' Friendship University of Russia (RU)
- St Petersburg University (RU)
- Russian New University (RU)
- A.E. Favorsky Irkutsk Institute of Chemistry (RU)
- Siberian Branch of the Russian Academy of Sciences (RU)
- Nikolaev Institute of Inorganic Chemistry (RU)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-09-09
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c02593
- Citations
- 5
- Primary Topic
- Crystallography and molecular interactions
- Type
- article
- Field-Weighted Citation Impact
- 2.22
Funders
- Russian Science Foundation