Vanadium O-Centered Selenoiodide Complex: Synthesis and Structure of V4O(Se2)4I6·I2

Sofya Artemkina; Ruslan Galiev; Pavel Poltarak; Vladislav Komarov; Yakov Gayfulin; Alexander Lavrov; Vladimir Fedorov

doi:10.1021/acs.inorgchem.1c02213

Vanadium O-Centered Selenoiodide Complex: Synthesis and Structure of V₄O(Se₂)₄I₆·I₂

Inorg Chem. 2021 Dec 6;60(23):17627-17634. doi: 10.1021/acs.inorgchem.1c02213. Epub 2021 Nov 11.

Authors

Sofya Artemkina¹, Ruslan Galiev¹, Pavel Poltarak¹, Vladislav Komarov¹, Yakov Gayfulin¹, Alexander Lavrov¹, Vladimir Fedorov¹

Affiliation

¹ Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Akad. Lavrentiev Avenue, Novosibirsk 630090, Russia.

PMID: 34761921
DOI: 10.1021/acs.inorgchem.1c02213

Abstract

The first vanadium selenoiodide V₄O(Se₂)₄I₆·I₂ was synthesized at a moderate temperature of 220 °C from V, Se, I₂, and water. Its crystal structure (tetragonal space group P4₂/nbc, a = 11.838(1) Å, c = 18.689(1) Å) contains O-centered vanadium(IV) tetranuclear fragment [V₄(μ₄-O)(μ₂-Se₂)₄(μ₂-I)₂I₄], where the edges of the distorted tetrahedron V₄ are bridged by four diselenide (Se₂)^2- and two iodide ligands; four terminal iodides coordinate V atoms additionally. This type of complex is known for Ti, Nb, and Ta but is new for vanadium. Magnetic susceptibility measurements of V₄O(Se₂)₄I₆·I₂ showed four unpaired electrons on vanadium atoms at room temperature and drop of the effective magnetic moment at cool down, presumably due to partial electron pairing. Probability of this transition to the diamagnetic state is in accord with the calculated electronic structure.