Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

Andrey N Usoltsev; Taisiya S Sukhikh; Alexander S Novikov; Vladimir R Shayapov; Denis P Pishchur; Ilya V Korolkov; Ilyas F Sakhapov; Vladimir P Fedin; Maxim N Sokolov; Sergey A Adonin

doi:10.1021/acs.inorgchem.0c03699

Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

Inorg Chem. 2021 Feb 15;60(4):2797-2804. doi: 10.1021/acs.inorgchem.0c03699. Epub 2021 Jan 26.

Affiliations

¹ Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St., 630090 Novosibirsk, Russia.
² Saint Petersburg State University, Universitetskaya Nab., 7/9, 199034 Saint Petersburg, Russia.
³ South Ural State University, Lenina St. 76, 454080 Chelyabinsk, Russia.

PMID: 33496171
DOI: 10.1021/acs.inorgchem.0c03699

Abstract

Reactions of [SbBr₆]^3- containing HBr solutions with bromide salts of 1,1'-(1,2-ethanediyl)bis(pyridine) (PyC₂²⁺) or 1,1'-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePyC₂²⁺) initially result in the formation of the deep orange complexes Cat[SbBr₅] (1 and 2), featuring unusual Sb···Br interactions in the solid state. In the mother liquor, 1 transforms into discrete binuclear (C₂Py)₂[Sb₂Br₁₀], which demonstrates polymorphism (triclinic 3 and monoclinic 4), while 2 transforms into polymeric (3,5-MePy){[SbBr₄]} (5). DFT calculations reveal that the system of noncovalent Sb···Br contacts may be responsible for the appearance of the observed optical properties (unusual deep orange coloring).