Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)2(µ‒O)}3+ core: Theoretical and experimental insights

Richa; Akhilesh Kumar; Indresh Verma; Mamta Gautam; Rohan D. Erande; Julia Kłak; Duane Choquesillo-Lazarte; Antonio J. Mota; Amit Rajput; Himanshu Arora

doi:10.1016/j.molstruc.2022.133805

Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)₂(µ‒O)}³⁺ core: Theoretical and experimental insights

Richa, Akhilesh Kumar, Indresh Verma, Mamta Gautam, Rohan D. Erande, Julia Kłak, Duane Choquesillo-Lazarte, Antonio J. Mota, Amit Rajput, Himanshu Arora

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Using deprotonated forms of tetradentate phenol amine ligands 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol (HL¹), dinuclear vanadium(IV,V) complex of composition [(L¹)₂(V^IVO)(µ-O)(V^VO)](ClO₄) (1) was synthesized and characterized by X–ray crystallography, UV–Vis, EPR and magnetic susceptibility measurements. Direct current (DC) variable-temperature magnetic susceptibility measurements on polycrystalline sample of 1 were carried out in the temperature range 1.8–300 K. Electron paramagnetic resonance and magnetic studies for 1 demonstrated the complete localization of the single 3d electron on one of vanadium ion and very weak antiferromagnetic interaction between the paramagnetic vanadium(IV) ions in the crystal lattice. The cyclic voltammogram observed with 1, revealed one oxidation process which is tentatively assigned to V^IVV^V/V₂^V. [(L¹)₂(V^VO)₂(µ-O)](ClO₄)₂ (2.2.5CH₂Cl₂) has been synthesized chemically from 1 and were thoroughly characterized by X–ray crystallography, UV–Vis, ⁵¹V NMR and IR measurements.

Original language	English
Article number	133805
Journal	Journal of Molecular Structure
Volume	1269
DOIs	https://doi.org/10.1016/j.molstruc.2022.133805
State	Published - 5 Dec 2022
Externally published	Yes

Bibliographical note

Funding Information:
Authors thank Prof. R.N. Mukherjee for using the lab facilities at IIT Kanpur. Authors also thank the CSIRC/ALHAMBRA supercomputing center of the Universidad de Granada for computational resources.

Publisher Copyright:
© 2022 Elsevier B.V.

Keywords

DFT calculations
EPR spectroscopy
Magnetic properties
Mixed-valence
Redox properties
Vanadium complexes
X-ray diffraction

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10.1016/j.molstruc.2022.133805

Cite this

Richa, Kumar, A., Verma, I., Gautam, M., Erande, R. D., Kłak, J., Choquesillo-Lazarte, D., Mota, A. J., Rajput, A., & Arora, H. (2022). Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)₂(µ‒O)}³⁺ core: Theoretical and experimental insights. Journal of Molecular Structure, 1269, [133805]. https://doi.org/10.1016/j.molstruc.2022.133805

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title = "Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)2(µ‒O)}3+ core: Theoretical and experimental insights",

abstract = "Using deprotonated forms of tetradentate phenol amine ligands 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol (HL1), dinuclear vanadium(IV,V) complex of composition [(L1)2(VIVO)(µ-O)(VVO)](ClO4) (1) was synthesized and characterized by X–ray crystallography, UV–Vis, EPR and magnetic susceptibility measurements. Direct current (DC) variable-temperature magnetic susceptibility measurements on polycrystalline sample of 1 were carried out in the temperature range 1.8–300 K. Electron paramagnetic resonance and magnetic studies for 1 demonstrated the complete localization of the single 3d electron on one of vanadium ion and very weak antiferromagnetic interaction between the paramagnetic vanadium(IV) ions in the crystal lattice. The cyclic voltammogram observed with 1, revealed one oxidation process which is tentatively assigned to VIVVV/V2V. [(L1)2(VVO)2(µ-O)](ClO4)2 (2.2.5CH2Cl2) has been synthesized chemically from 1 and were thoroughly characterized by X–ray crystallography, UV–Vis, 51V NMR and IR measurements.",

keywords = "DFT calculations, EPR spectroscopy, Magnetic properties, Mixed-valence, Redox properties, Vanadium complexes, X-ray diffraction",

author = "Richa and Akhilesh Kumar and Indresh Verma and Mamta Gautam and Erande, {Rohan D.} and Julia K{\l}ak and Duane Choquesillo-Lazarte and Mota, {Antonio J.} and Amit Rajput and Himanshu Arora",

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year = "2022",

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doi = "10.1016/j.molstruc.2022.133805",

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Richa, Kumar, A, Verma, I, Gautam, M, Erande, RD, Kłak, J, Choquesillo-Lazarte, D, Mota, AJ, Rajput, A & Arora, H 2022, 'Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)₂(µ‒O)}³⁺ core: Theoretical and experimental insights', Journal of Molecular Structure, vol. 1269, 133805. https://doi.org/10.1016/j.molstruc.2022.133805

TY - JOUR

T1 - Structural and magnetic characterization of mixed-valence vanadium (IV/V) complex with {(VO)2(µ‒O)}3+ core

T2 - Theoretical and experimental insights

AU - Richa,

AU - Kumar, Akhilesh

AU - Verma, Indresh

AU - Gautam, Mamta

AU - Erande, Rohan D.

AU - Kłak, Julia

AU - Choquesillo-Lazarte, Duane

AU - Mota, Antonio J.

AU - Rajput, Amit

AU - Arora, Himanshu

PY - 2022/12/5

Y1 - 2022/12/5

N2 - Using deprotonated forms of tetradentate phenol amine ligands 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol (HL1), dinuclear vanadium(IV,V) complex of composition [(L1)2(VIVO)(µ-O)(VVO)](ClO4) (1) was synthesized and characterized by X–ray crystallography, UV–Vis, EPR and magnetic susceptibility measurements. Direct current (DC) variable-temperature magnetic susceptibility measurements on polycrystalline sample of 1 were carried out in the temperature range 1.8–300 K. Electron paramagnetic resonance and magnetic studies for 1 demonstrated the complete localization of the single 3d electron on one of vanadium ion and very weak antiferromagnetic interaction between the paramagnetic vanadium(IV) ions in the crystal lattice. The cyclic voltammogram observed with 1, revealed one oxidation process which is tentatively assigned to VIVVV/V2V. [(L1)2(VVO)2(µ-O)](ClO4)2 (2.2.5CH2Cl2) has been synthesized chemically from 1 and were thoroughly characterized by X–ray crystallography, UV–Vis, 51V NMR and IR measurements.

AB - Using deprotonated forms of tetradentate phenol amine ligands 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol (HL1), dinuclear vanadium(IV,V) complex of composition [(L1)2(VIVO)(µ-O)(VVO)](ClO4) (1) was synthesized and characterized by X–ray crystallography, UV–Vis, EPR and magnetic susceptibility measurements. Direct current (DC) variable-temperature magnetic susceptibility measurements on polycrystalline sample of 1 were carried out in the temperature range 1.8–300 K. Electron paramagnetic resonance and magnetic studies for 1 demonstrated the complete localization of the single 3d electron on one of vanadium ion and very weak antiferromagnetic interaction between the paramagnetic vanadium(IV) ions in the crystal lattice. The cyclic voltammogram observed with 1, revealed one oxidation process which is tentatively assigned to VIVVV/V2V. [(L1)2(VVO)2(µ-O)](ClO4)2 (2.2.5CH2Cl2) has been synthesized chemically from 1 and were thoroughly characterized by X–ray crystallography, UV–Vis, 51V NMR and IR measurements.

KW - DFT calculations

KW - EPR spectroscopy

KW - Magnetic properties

KW - Mixed-valence

KW - Redox properties

KW - Vanadium complexes

KW - X-ray diffraction

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