Magnetostructural relationships in [Ni(dmit)<sub>2</sub>]<sup>−</sup>radical anions

Zapata-Rivera, Jhon; Calzado, Carmen J.

doi:10.1039/d1dt00734c

Cited by 5 publications

(3 citation statements)

References 47 publications

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“…In every case, we give priority to the Fe atom. We have previously used a similar strategy to evaluate the activation of O 2 , − the magnetic coupling of dinuclear systems, , as well as other kinds of problems. , …”

Section: Methodsmentioning

confidence: 99%

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Zapata-Rivera,

Calzado

2024

Inorg. Chem.

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Herein, we report the estimation of the extent of dinitrogen activation by different charged and structural forms of (P 2 P Ph )Fe biomimetic catalysts, which, in the presence of light, exhibit significant yield in the N 2 -to-NH 3 conversion. Complete active space self-consistent field (CASSCF) calculations have been used to determine the electronic structure of different reduced forms of the mononuclear complexes: the neutral (P 2 P Ph )Fe(N 2 ) 2 adduct and the anionic [(P 2 P Ph )Fe(N 2 )] − and [(P 2 P Ph )Fe(N 2 )] 2− complexes. These calculations also revealed that the extent of reduction of a dinitrogen molecule reaches up to one electron (N 2 1− ) due to the back-bonding from the Fe center, in agreement with the changes observed in the vibration frequency of the N−N bond in these complexes. In addition, the energy profile of the dimerization of the mononuclear (P 2 P Ph )Fe(N 2 ) 2 complex to the dinuclear mono-N 2 -bridged [(P 2 P Ph )Fe] 2 (μ−N 2 ) complex has been determined by means of density functional theory (DFT) calculations. A three-step mechanism has been proposed for the dimerization, favored by both kinetics and thermodynamics criteria. Finally, the magnetic coupling constant in the diiron (μ−N 2 ) complex is estimated from CASSCF/NEVPT2 calculations. Such a dinuclear complex presents a strong antiferromagnetic coupling resulting from the interaction between two S = 1 d 6 Fe 2+ ions, bridged by a highly activated dinitrogen molecule (N 2 2−) with two electrons on the π* orbitals.

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Section: Methodsmentioning

confidence: 99%

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Zapata-Rivera,

Calzado

2024

Inorg. Chem.

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“…mnt 2À = maleonitriledithiolate dmit 2À = 2-thioxo-1,3-dithiole-4,5-dithiolate) with unique electronic structures and physical properties, have been intensively studied. [18][19][20][21][22][23][24][25][26][27] Too much research effort towards the development of [M(mnt)] À and [M(dmit)] À compounds by rational design of the counter ion structure has been reported. For instance, Nakamura's group [20][21][22] reported the incorporation of a supramolecular M-crown ether cation into the [Ni(dmit) 2 ] À system to yield a molecular metal complex with magnetic and conducting properties and ferroelectricity.…”

Section: Introductionmentioning

confidence: 99%

Halogen substitution effects on crystal structures and magnetic properties in nickel dithiolate molecular crystals

Chen,

Wei

et al. 2024

New J. Chem.

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“…The exchange coupling between paramagnetic centers has been a subject of such investigations at the density functional theory (DFT) and ab initio levels, but these studies were mainly limited to the interaction between metallic centers [ 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 ]. Theoretical studies on the exchange coupling between radical ligands and paramagnetic metal ions were performed [ 77 , 78 , 79 , 80 , 81 ]. However, in our opinion, a systematic understanding of how various structural and electronic features of such complexes affect exchange coupling is still lacking.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

Ziółkowska

Witwicki

2023

IJMS

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The exchange coupling, represented by the J parameter, is of tremendous importance in understanding the reactivity and magnetic behavior of open-shell molecular systems. In the past, it was the subject of theoretical investigations, but these studies are mostly limited to the interaction between metallic centers. The exchange coupling between paramagnetic metal ions and radical ligands has hitherto received scant attention in theoretical studies, and thus the understanding of the factors governing this interaction is lacking. In this paper, we use DFT, CASSCF, CASSCF/NEVPT2, and DDCI3 methods to provide insight into exchange interaction in semiquinonato copper(II) complexes. Our primary objective is to identify structural features that affect this magnetic interaction. We demonstrate that the magnetic character of Cu(II)-semiquinone complexes are mainly determined by the relative position of the semiquinone ligand to the Cu(II) ion. The results can support the experimental interpretation of magnetic data for similar systems and can be used for the in-silico design of magnetic complexes with radical ligands.

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Magnetostructural relationships in [Ni(dmit)₂]⁻radical anions

Abstract: This work explores the relationship between the magnetic properties of salts based on the [Ni(dmit)2]− radicals and the different arrangement that these radicals can adopt in the crystals, induced by...

Cited by 5 publications

References 47 publications

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Halogen substitution effects on crystal structures and magnetic properties in nickel dithiolate molecular crystals

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

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Magnetostructural relationships in [Ni(dmit)2]−radical anions

Abstract: This work explores the relationship between the magnetic properties of salts based on the [Ni(dmit)2]− radicals and the different arrangement that these radicals can adopt in the crystals, induced by...

Cited by 5 publications

References 47 publications

Dinitrogen Activation Mediated by the (P2PPh)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Dinitrogen Activation Mediated by the (P2PPh)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Halogen substitution effects on crystal structures and magnetic properties in nickel dithiolate molecular crystals

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes

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Product

Resources

About

Magnetostructural relationships in [Ni(dmit)₂]⁻radical anions

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling

Dinitrogen Activation Mediated by the (P₂P^Ph)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling