TY - JOUR

T1 - Characterization of the O-centered vanadium selenoiodides V4OSe8I6·X (X = I2, 3,5-dimethylpyrazole)

AU - Galiev, R. R.

AU - Komarov, V. Y.

AU - Khisamov, R. M.

AU - Ledneva, A. Yu

AU - Artemkina, S. B.

AU - Fedorov, V. E.

N1 - This work was carried out with the financial support of the Russian Science Foundation (project RSF No. 21-13-00274, https://rscf.ru/project/21-13-00274/). The authors also thank XRD Facility of Nikolaev Institute of Inorganic Chemistry SB RAS for the SC XRD data collection (Ministry of Science and Higher Education of the Russian Federation, N 121031700313-8) and Novosibirsk State University Supercomputer Center for providing supercomputer facility.

PY - 2023/4/1

Y1 - 2023/4/1

N2 - O-centered vanadium(IV) selenoiodide V4OSe8I6·3,5-dimethylpyrazole was synthesized in a sealed glass ampoule at moderate temperature 220 °C from the mixture of V, Se, I2, small quantity of water and 3,5-dimethylpyrazole. The X-ray single crystal structure of the compound was solved. The crystal structure includes O-centered tetranuclear complex [V4(μ4-O)(μ-Se2)4(μ-I)2I4] in which vanadium atoms are bridged by diselenide (Se2)2– and iodide I– groups; four terminal iodides coordinate vanadium atoms additionally. Molecules of 3,5-dimethylpyrazole form non-covalent contacts with iodine and selenium atoms of the V4OSe8I6 complexes. Once compounds V4OSe8I6·3,5-dimethylpyrazole and V4OSe8I6·I2 contain similar electroneutral coordination molecular fragment V4OSe8I6, we present here a discussion of spectroscopic properties as well as thermal behavior. Comparing XPS data, both compounds contain vanadium complexes with major V 2p binding energies very similar to each other, and almost equal binding energies in XPS Se 3d and I 3d showing their forms of (Se2–)2 and I–, respectively. Thermolysis character of these compounds revealed higher stability of V4OSe8I6·I2 than V4OSe8I6·3,5-dimethylpyrazole, that indicates a greater stability of the system of non-covalent contacts involving iodine molecules than 3,5-dimethylpyrazole.

AB - O-centered vanadium(IV) selenoiodide V4OSe8I6·3,5-dimethylpyrazole was synthesized in a sealed glass ampoule at moderate temperature 220 °C from the mixture of V, Se, I2, small quantity of water and 3,5-dimethylpyrazole. The X-ray single crystal structure of the compound was solved. The crystal structure includes O-centered tetranuclear complex [V4(μ4-O)(μ-Se2)4(μ-I)2I4] in which vanadium atoms are bridged by diselenide (Se2)2– and iodide I– groups; four terminal iodides coordinate vanadium atoms additionally. Molecules of 3,5-dimethylpyrazole form non-covalent contacts with iodine and selenium atoms of the V4OSe8I6 complexes. Once compounds V4OSe8I6·3,5-dimethylpyrazole and V4OSe8I6·I2 contain similar electroneutral coordination molecular fragment V4OSe8I6, we present here a discussion of spectroscopic properties as well as thermal behavior. Comparing XPS data, both compounds contain vanadium complexes with major V 2p binding energies very similar to each other, and almost equal binding energies in XPS Se 3d and I 3d showing their forms of (Se2–)2 and I–, respectively. Thermolysis character of these compounds revealed higher stability of V4OSe8I6·I2 than V4OSe8I6·3,5-dimethylpyrazole, that indicates a greater stability of the system of non-covalent contacts involving iodine molecules than 3,5-dimethylpyrazole.

KW - Selenoiodide

KW - Tetranuclear complex

KW - Vanadium

KW - Vibrational spectroscopy

KW - X-ray photoelectron spectroscopy

KW - X-ray single crystal structure

UR - https://www.scopus.com/inward/record.url?eid=2-s2.0-85145862393&partnerID=40&md5=9c4577d1a3f0209477b749405b84cb3b

UR - https://www.mendeley.com/catalogue/78e75cd6-0220-376c-827f-24d891f76a7e/

U2 - 10.1016/j.ica.2022.121366

DO - 10.1016/j.ica.2022.121366

M3 - Article

VL - 548

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 121366

ER -