Extended chains in vanadium O-centered complex [V4OSe8I5]∞: synthesis and structure

Extended chains in vanadium O-centered complex [V4OSe8I5]∞: synthesis and structure Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2025, Volume: 54, Number: 5, Pages: 2147-2155 Pages count : 9 DOI: 10.1039/D4DT02758B

Authors

Galiev R.R. ¹ , Komarov V.Y. ¹ , Ryzhikov M.R. ¹ , Kozlova S.G. ¹ , Kuznetsov V.A. ¹ , Grayfer E.D. ^1,2 , Artemkina S.B. ¹ , Fedorov V.E. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Akad. Lavrentiev Ave., Novosibirsk 630090, Russia
2	Center for Photonic Science and Engineering (CPhSE), Skolkovo Institute of Science and Technology, 3 Nobel Street, Moscow, 121205 Russian Federation

O-centered tetranuclear vanadium selenoiodide [V4OSe8I5]∞ (1) was synthesized by an ampoule method from the elements with addition of water. Its X-ray crystal structure (space group C2/c, a = 21.146(2) Å, b = 5.8953(5) Å, c = 18.735(1) Å, β = 126.421(2)°, V = 1879.4(3) Å3, T = 150 K, Z = 4) is a packing of chains built from O-centered tetranuclear [V4(μ4-O)(μ-Se2)4(μ4-I)2/2I4] fragments. In the O-centered fragment, vanadium atoms form a distorted tetrahedron around an oxygen atom, V atoms are bridged by four μ2-(Se2)2− and two I− ligands. The latter iodide ligands bridge the neighboring fragments, thus forming a chain [V4(μ4-O)(μ-Se2)4(μ4-I)2/2I4]∞. The synthesis of the chain [V4OSe8I5]∞ takes place at the temperature of 290 °C, while at lower temperatures (220–250 °C) molecular compounds [V4OSe8I6]·X form. The direct ‘cluster to chain’ transformation is also observed and discussed in this work. Electrical resistance of the [V4OSe8I5]∞ polycrystalline pressed sample shows that the compound 1 is a narrow gap semiconductor, which is in agreement with the DFT calculations.

Galiev R.R. , Komarov V.Y. , Ryzhikov M.R. , Kozlova S.G. , Kuznetsov V.A. , Grayfer E.D. , Artemkina S.B. , Fedorov V.E.
Extended chains in vanadium O-centered complex [V4OSe8I5]∞: synthesis and structure
Dalton Transactions. 2025. V.54. N5. P.2147-2155. DOI: 10.1039/D4DT02758B WOS OpenAlex

Submitted:	Oct 1, 2024
Accepted:	Dec 16, 2024
Published online:	Dec 17, 2024
Published print:	Feb 7, 2025

Web of science:	WOS:001380477100001
OpenAlex:	W4405476603

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