On the Control of Magnetic Anisotropy through an External Electric Field

Goswami, Tamal; Misra, Anirban

doi:10.1002/chem.201403370

Cited by 8 publications

(8 citation statements)

References 51 publications

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“…Thus, for understanding the effect of altering the ligand, a deeper insight from DFT is necessary. DFT calculations on all the geometries of complexes 1 , 2 , and 3 are performed with the respective Cl, Br, and NCS ligands replaced by point charges of magnitude −1.0 . This calculation, on one hand, shows the effect of altering geometries on the ligand substitution as is performed experimentally in a very straightforward and convincing way, while, on the other hand, it also shows the effect of individual ligands, i.e., Cl, Br, and NCS, on the value of the ZFS parameter.…”

Section: Resultsmentioning

confidence: 99%

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Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets

et al. 2017

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In this work, the effects of ligand field strength as well as the metal coordination geometry on magnetic anisotropy of pentacoordinated Co complexes have been investigated using a combined experimental and theoretical approach. For that, a strategic design and synthesis of three pentacoordinate Co complexes [Co(bbp)Cl]·(MeOH) (1), [Co(bbp)Br]·(MeOH) (2), and [Co(bbp)(NCS)] (3) has been achieved by using the tridentate coordination environment of the ligand in conjunction with the accommodating terminal ligands (i.e., chloride, bromide, and thiocyanate). Detailed magnetic studies disclose the occurrence of slow magnetic relaxation behavior of Co centers with an easy-plane magnetic anisotropy. A quantitative estimation of ZFS parameters has been successfully performed by density functional theory (DFT) calculations. Both the sign and magnitude of ZFS parameters are prophesied well by this DFT method. The theoretical results also reveal that the α → β (SOMO-SOMO) excitation contributes almost entirely to the total ZFS values for all complexes. It is worth noting that the excitation pertaining to the most positive contribution to the ZFS parameter is the d → d excitation for complexes 1 and 2, whereas for complex 3 it is the d → d excitation.

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Section: Resultsmentioning

confidence: 99%

“…Therefore, the DFT calculations on these complexes are in better agreement with the experimental results. Previous reports have also shown that DFT can calculate ZFS parameters for Co II complexes. ,− …”

Section: Resultsmentioning

confidence: 99%

Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets

et al. 2017

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“…As this has not been observed above 100 K, a long-lived X-ray induced excited spin-state trapping akin to optical excitations that give rise to LIESST is unlikely, but X-ray absorption spectroscopy does produce a significant photocurrent. For this reason, an electrostatic- ,,, or current-induced − transient switching the molecular spin state, in the vicinity of the spin crossover transition, is possible and might be associated with a change in the dielectric constant. Steric hindrance, including crystal packing, sample conductance, and flux density, would all then play a role in determining at what temperatures this transient, not necessarily even metastable, electronic transition would occur.…”

Section: Concordance Of the Electronic And Magnetic States ?mentioning

confidence: 99%

Complexities in the Molecular Spin Crossover Transition

Zhang

Chastanet

et al. 2015

J. Phys. Chem. C

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International audienceVariable-temperature studies of the electronic structures of four different Fe(II) spin crossover molecules, [Fe(H2B(pz)2)2(bipy)] (pz = pyrazol-1-yl, bipy = 2,2′-bipyridine), [Fe(H2B(pz)2)2(phen)], [Fe(phen)2(NCS)2] (phen = 9,10-phenantroline), and [Fe(PM-AzA)2(NCS)2] (PM-AzA = 4-phenyldiazenyl-N-(pyridin-2-ylmethylene)aniline) by X-ray absorption spectroscopy (XAS), combined with electrical properties studies of the [Fe(PM-AzA)2(NCS)2] single crystal are presented. We show that both the XAS signature of the spin state of powdered samples and the dielectric permittivity of the [Fe(PM-AzA)2(NCS)2] single crystal change at significantly lower temperatures than the magnetometry, structure, and resistivity indicators of a spin crossover transition. The changes in electronic structure are in agreement with the expectations from density functional theory (DFT) results for the different molecular electronic structures associated with the high-spin and low-spin states. These findings suggest that the electronic structure phase ordering process does not simply follow the spin transition

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“…An external electric field (EEF) can modulate the nature and strength of intermolecular interactions, [1][2][3][4] affect the products of known chemical processes, [5][6][7][8][9] energies of the electronic states 10,11 and consequently response properties of molecules. [12][13][14][15] The EEF has been employed for molecular sensing 16,17 and recently for catalysis. [18][19][20] Carbon nanostructures, in particular graphene, 21 because of their polarizable extended p-systems are a fascinating class of materials whose properties can be influenced considerably by means of an EEF.…”

Section: Introductionmentioning

confidence: 99%

Solvent effects on ion–receptor interactions in the presence of an external electric field

Novák

Foroutan‐Nejad

Marek

2016

Phys. Chem. Chem. Phys.

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In this work we investigated the influence of an external electric field on the arrangement of the solvent shells around ions interacting with a carbon-based receptor. Our survey reveals that the mechanism of interaction between a monoatomic ion and a π-type ion receptor varies by the variation in the solvent polarity, the nature of the ion, and the strength of the external field. The characteristics of the ion-surface interaction in nonpolar solvents are similar to those observed in a vacuum. However, in water, we identified two mechanisms. Soft and polarizable ions preferentially interact with the π-receptor. In contrast, two bonded states were found for hard ions. A fully solvated ion, weakly interacting with the receptor at weak field, and a strong π-complex at the strong-field regime were identified. An abrupt variation in the potential energy surface (PES) associated with the rearrangement of the solvation shell on the surface of the receptor induced by an external field was observed both in implicit and explicit solvent environments. The electric field at which the solvation shell breaks is proportional to the hardness of the ion as has been suggested recently based on experimental observations.

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On the Control of Magnetic Anisotropy through an External Electric Field

Cited by 8 publications

References 51 publications

Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets

Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets

Complexities in the Molecular Spin Crossover Transition

Solvent effects on ion–receptor interactions in the presence of an external electric field

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