Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights

Richa; Akhilesh Kumar; Indresh Verma; Pankaj Garg; Rohan D. Erande; Saleem Javed; Amit Rajput; Carlos J.Gomez Garcia; Antonio J. Mota; Himanshu Arora

doi:10.1016/j.molstruc.2023.135426

Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights

Richa, Akhilesh Kumar, Indresh Verma, Pankaj Garg, Rohan D. Erande, Saleem Javed, Amit Rajput, Carlos J.Gomez Garcia, Antonio J. Mota, Himanshu Arora

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Abstract

Three dinuclear complexes of formula [Fe^III₂(µ-O)(µ-OOCR)(L)₂](ClO₄)·G, with R/G=H/(EtOAc)₂ (1·2EtOAc), CH₃/(Et₂O)₂ (2·2Et₂O) and C₆H₅/(CH₃OH)₂(CH₃CN)₂ (3·2CH₃OH·2CH₃CN), [where HL = 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol] have been prepared. The ligand provides a N,N,N,O donor set in its deprotonated form. X-ray diffraction analyses revealed that the complexes have a similar oxido-carboxylato-bridged structure where each metal ion has a tertiary amine, one imidazolyl N atom, one pyridyl N atom and a phenolate O atom as terminal coordination. Thus, each metal centre assumes a Fe^IIIN₃O₃ coordination in an octahedral environment. Addition of acid lead to the generation of similar dinuclear complexes formulated as [Fe^III₂(µ-OH)(µ-OOCR)(L)₂](ClO₄)₂, with R=H (1^H), CH₃ (2^H) and C₆H₅ (3^H) in solution. This protonation of the µ-O bridge is reversible and addition of base regenerates the original complexes (1–3). Magnetic measurements showed intramolecular antiferromagnetic Fe···Fe interactions in compounds 1–3 with J = ‒276(1), ‒197(1) and ‒190(1) cm⁻¹, respectively. DFT/B3LYP calculation helped us to explicitly state the sign and magnitude of the magnetic coupling constants along with an approaching to the spin density distribution.

Original language	English
Article number	135426
Journal	Journal of Molecular Structure
Volume	1285
DOIs	https://doi.org/10.1016/j.molstruc.2023.135426
State	Published - 5 Aug 2023
Externally published	Yes

Bibliographical note

Funding Information:
The authors thank Prof. R. N. Mukherjee for use of the lab facilities at IIT Kanpur. The authors also thank the CSIRC/ ALHAMBRA supercomputing centre for quantum chemistry software and calculation time. This study forms part of the Advanced Materials program and was supported by the Spanish MCIN with funding from European Union NextGeneration EU (PRTR-C17.I1) and the Generalitat Valenciana (project MFA-2022-057). We also thank the project PID2021-125907NB-I00, financed by MCIN/AEI/10.13039/501100011033/FEDER, UE, for financial support.

Funding Information:
The authors thank Prof. R. N. Mukherjee for use of the lab facilities at IIT Kanpur. The authors also thank the CSIRC/ ALHAMBRA supercomputing centre for quantum chemistry software and calculation time. This study forms part of the Advanced Materials program and was supported by the Spanish MCIN with funding from European Union NextGeneration EU (PRTR-C17.I1) and the Generalitat Valenciana (project MFA-2022-057). We also thank the project PID2021-125907NB-I00, financed by MCIN/AEI/10.13039/501100011033/FEDER, UE, for financial support.

Publisher Copyright:
© 2023 Elsevier B.V.

Keywords

Broken symmetry
DFT
Dinuclear iron complexes
Magnetic properties
Reversible interconversion
pH-controlled

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10.1016/j.molstruc.2023.135426

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Richa, Kumar, A., Verma, I., Garg, P., Erande, R. D., Javed, S., Rajput, A., Garcia, C. J. G., Mota, A. J., & Arora, H. (2023). Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights. Journal of Molecular Structure, 1285, [135426]. https://doi.org/10.1016/j.molstruc.2023.135426

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title = "Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights",

abstract = "Three dinuclear complexes of formula [FeIII2(µ-O)(µ-OOCR)(L)2](ClO4)·G, with R/G=H/(EtOAc)2 (1·2EtOAc), CH3/(Et2O)2 (2·2Et2O) and C6H5/(CH3OH)2(CH3CN)2 (3·2CH3OH·2CH3CN), [where HL = 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol] have been prepared. The ligand provides a N,N,N,O donor set in its deprotonated form. X-ray diffraction analyses revealed that the complexes have a similar oxido-carboxylato-bridged structure where each metal ion has a tertiary amine, one imidazolyl N atom, one pyridyl N atom and a phenolate O atom as terminal coordination. Thus, each metal centre assumes a FeIIIN3O3 coordination in an octahedral environment. Addition of acid lead to the generation of similar dinuclear complexes formulated as [FeIII2(µ-OH)(µ-OOCR)(L)2](ClO4)2, with R=H (1H), CH3 (2H) and C6H5 (3H) in solution. This protonation of the µ-O bridge is reversible and addition of base regenerates the original complexes (1–3). Magnetic measurements showed intramolecular antiferromagnetic Fe···Fe interactions in compounds 1–3 with J = ‒276(1), ‒197(1) and ‒190(1) cm−1, respectively. DFT/B3LYP calculation helped us to explicitly state the sign and magnitude of the magnetic coupling constants along with an approaching to the spin density distribution.",

keywords = "Broken symmetry, DFT, Dinuclear iron complexes, Magnetic properties, Reversible interconversion, pH-controlled",

author = "Richa and Akhilesh Kumar and Indresh Verma and Pankaj Garg and Erande, {Rohan D.} and Saleem Javed and Amit Rajput and Garcia, {Carlos J.Gomez} and Mota, {Antonio J.} and Himanshu Arora",

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doi = "10.1016/j.molstruc.2023.135426",

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Richa, Kumar, A, Verma, I, Garg, P, Erande, RD, Javed, S, Rajput, A, Garcia, CJG, Mota, AJ & Arora, H 2023, 'Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights', Journal of Molecular Structure, vol. 1285, 135426. https://doi.org/10.1016/j.molstruc.2023.135426

TY - JOUR

T1 - Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers

T2 - Theoretical and experimental insights

AU - Richa,

AU - Kumar, Akhilesh

AU - Verma, Indresh

AU - Garg, Pankaj

AU - Erande, Rohan D.

AU - Javed, Saleem

AU - Rajput, Amit

AU - Garcia, Carlos J.Gomez

AU - Mota, Antonio J.

AU - Arora, Himanshu

PY - 2023/8/5

Y1 - 2023/8/5

N2 - Three dinuclear complexes of formula [FeIII2(µ-O)(µ-OOCR)(L)2](ClO4)·G, with R/G=H/(EtOAc)2 (1·2EtOAc), CH3/(Et2O)2 (2·2Et2O) and C6H5/(CH3OH)2(CH3CN)2 (3·2CH3OH·2CH3CN), [where HL = 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol] have been prepared. The ligand provides a N,N,N,O donor set in its deprotonated form. X-ray diffraction analyses revealed that the complexes have a similar oxido-carboxylato-bridged structure where each metal ion has a tertiary amine, one imidazolyl N atom, one pyridyl N atom and a phenolate O atom as terminal coordination. Thus, each metal centre assumes a FeIIIN3O3 coordination in an octahedral environment. Addition of acid lead to the generation of similar dinuclear complexes formulated as [FeIII2(µ-OH)(µ-OOCR)(L)2](ClO4)2, with R=H (1H), CH3 (2H) and C6H5 (3H) in solution. This protonation of the µ-O bridge is reversible and addition of base regenerates the original complexes (1–3). Magnetic measurements showed intramolecular antiferromagnetic Fe···Fe interactions in compounds 1–3 with J = ‒276(1), ‒197(1) and ‒190(1) cm−1, respectively. DFT/B3LYP calculation helped us to explicitly state the sign and magnitude of the magnetic coupling constants along with an approaching to the spin density distribution.

AB - Three dinuclear complexes of formula [FeIII2(µ-O)(µ-OOCR)(L)2](ClO4)·G, with R/G=H/(EtOAc)2 (1·2EtOAc), CH3/(Et2O)2 (2·2Et2O) and C6H5/(CH3OH)2(CH3CN)2 (3·2CH3OH·2CH3CN), [where HL = 2-((((1-methylbenzimidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol] have been prepared. The ligand provides a N,N,N,O donor set in its deprotonated form. X-ray diffraction analyses revealed that the complexes have a similar oxido-carboxylato-bridged structure where each metal ion has a tertiary amine, one imidazolyl N atom, one pyridyl N atom and a phenolate O atom as terminal coordination. Thus, each metal centre assumes a FeIIIN3O3 coordination in an octahedral environment. Addition of acid lead to the generation of similar dinuclear complexes formulated as [FeIII2(µ-OH)(µ-OOCR)(L)2](ClO4)2, with R=H (1H), CH3 (2H) and C6H5 (3H) in solution. This protonation of the µ-O bridge is reversible and addition of base regenerates the original complexes (1–3). Magnetic measurements showed intramolecular antiferromagnetic Fe···Fe interactions in compounds 1–3 with J = ‒276(1), ‒197(1) and ‒190(1) cm−1, respectively. DFT/B3LYP calculation helped us to explicitly state the sign and magnitude of the magnetic coupling constants along with an approaching to the spin density distribution.

KW - Broken symmetry

KW - DFT

KW - Dinuclear iron complexes

KW - Magnetic properties

KW - Reversible interconversion

KW - pH-controlled

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Magnetic properties and pH-controlled reversible interconversion of µ-oxido into µ-hydroxido in oxo-carboxylato bridged iron(III) dimers: Theoretical and experimental insights

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