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Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV). / Fedorenko, A. D.; Fomenko, I. S.; Gongola, M. I. et al.

In: Journal of Structural Chemistry, Vol. 62, No. 10, 10.2021, p. 1531-1542.

Research output: Contribution to journalArticlepeer-review

Harvard

Fedorenko, AD, Fomenko, IS, Gongola, MI, Pervukhina, NV, Kalinkin, AV, Nikolenko, AD & Gushchin, AL 2021, 'Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV)', Journal of Structural Chemistry, vol. 62, no. 10, pp. 1531-1542. https://doi.org/10.1134/S0022476621100073

APA

Fedorenko, A. D., Fomenko, I. S., Gongola, M. I., Pervukhina, N. V., Kalinkin, A. V., Nikolenko, A. D., & Gushchin, A. L. (2021). Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV). Journal of Structural Chemistry, 62(10), 1531-1542. https://doi.org/10.1134/S0022476621100073

Vancouver

Fedorenko AD, Fomenko IS, Gongola MI, Pervukhina NV, Kalinkin AV, Nikolenko AD et al. Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV). Journal of Structural Chemistry. 2021 Oct;62(10):1531-1542. doi: 10.1134/S0022476621100073

Author

Fedorenko, A. D. ; Fomenko, I. S. ; Gongola, M. I. et al. / Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV). In: Journal of Structural Chemistry. 2021 ; Vol. 62, No. 10. pp. 1531-1542.

BibTeX

@article{964ab4d959644fafa9449bb698042be3,
title = "Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV)",
abstract = "The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) {\AA}, b = 25.2962(4) {\AA}, с = 32.5478(6) {\AA}, V = 19112.8(6) {\AA}3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.",
keywords = "electronic structure, niobium, rhodanide, single crystal XRD, sulfide clusters, X-ray electron spectroscopy, XANES, XPS",
author = "Fedorenko, {A. D.} and Fomenko, {I. S.} and Gongola, {M. I.} and Pervukhina, {N. V.} and Kalinkin, {A. V.} and Nikolenko, {A. D.} and Gushchin, {A. L.}",
note = "Publisher Copyright: {\textcopyright} 2021, Pleiades Publishing, Ltd.",
year = "2021",
month = oct,
doi = "10.1134/S0022476621100073",
language = "English",
volume = "62",
pages = "1531--1542",
journal = "Journal of Structural Chemistry",
issn = "0022-4766",
publisher = "Springer GmbH & Co, Auslieferungs-Gesellschaf",
number = "10",

}

RIS

TY - JOUR

T1 - Crystal srtucture and X-ray crystallographic analysis of the binuclear cluster thiocyanate complex of niobium(IV)

AU - Fedorenko, A. D.

AU - Fomenko, I. S.

AU - Gongola, M. I.

AU - Pervukhina, N. V.

AU - Kalinkin, A. V.

AU - Nikolenko, A. D.

AU - Gushchin, A. L.

N1 - Publisher Copyright: © 2021, Pleiades Publishing, Ltd.

PY - 2021/10

Y1 - 2021/10

N2 - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) Å, b = 25.2962(4) Å, с = 32.5478(6) Å, V = 19112.8(6) Å3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.

AB - The structure of a binuclear niobium(IV) thiocyanate complex (Bu4N)4[Nb2(μ2-S2)2(NCS)8]·H2O (1·H2O) is studied by X-ray crystallography. Compound 1·H2O crystallizes in the orthorhombic crystal system (space group Pbca) with unit cell parameters a = 23.2139(4) Å, b = 25.2962(4) Å, с = 32.5478(6) Å, V = 19112.8(6) Å3, R = 0.0592. The electronic structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] complexes are investigated by X-ray spectroscopy techniques and compared with the structures of polymeric chalcogenides Nb2S4Br4 and Nb2Se4Br4. By XPS it is shown that effective charges on atoms of the {Nb2(μ-Q2)2}4+ (Q = S, Se) core do not change when passing from Br– to NCS– ligands. The HOMO and LUMO structures of (Bu4N)4[Nb2(μ2-S2)2(NCS)8] and (Bu4N)4[Nb2(μ2-Se2)2(NCS)8] are analyzed by XPS and XANES techniques. The largest contributions of S 3p states of NCS– ligands to the occupied molecular orbitals are found to be near the upper boundary of the valence band while the contributions from dichalcogenide bridging ligands have a more uniform distribution. For the conduction band, the contributions of S 3p states of NCS– ligands are located deeper whereas the contributions from dichalcogenide bridging ligands are near the lower boundary of the conduction band. The interaction of Nb 4d and S 3p/Se 4p states of dichalcogenide bridges for the HOMO has an antibonding character, which is bonding for all the other occupied molecular orbitals and antibonding for all unoccupied molecular orbitals.

KW - electronic structure

KW - niobium

KW - rhodanide

KW - single crystal XRD

KW - sulfide clusters

KW - X-ray electron spectroscopy

KW - XANES

KW - XPS

UR - http://www.scopus.com/inward/record.url?scp=85119137113&partnerID=8YFLogxK

U2 - 10.1134/S0022476621100073

DO - 10.1134/S0022476621100073

M3 - Article

AN - SCOPUS:85119137113

VL - 62

SP - 1531

EP - 1542

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 10

ER -

ID: 34679259