How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(<scp>ii</scp>) complexes

Rabelo, Renato; Toma, Luminita; Julve, Miguel; Lloret, Francesc; Pasán, Jorge; Cangussu, Danielle; Ruiz-García, Rafael; Cano, Joan

doi:10.1039/d4dt00059e

Dalton Trans.

2024

DOI: 10.1039/d4dt00059e

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How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(ii) complexes

Renato Rabelo,

Luminita Toma,

Miguel Julve

et al.

Abstract: A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1–3) and 3 (4); X...

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Cited by 5 publications

References 102 publications

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Temperature‐Driven Axial‐Equatorial Isomerism and Magnetic Relaxation on Low‐Spin Co(II) Borohydride Complexes

Wang,

Li,

Zhang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryCrystalline materials with diastereomerism serve as ideal prototypes for investigating the influence of coordination environments on chemophysical properties. In this study, we synthesized a pair of axial‐equatorial isomers [Co(II)(HB(timtBu)3)(cis‐dppen)](BF4)·solv ([HB(timtBu)3]− = hydrotris(3‐tertbutyl‐2‐thioxoimidazol‐1‐yl)borate; cis‐dppen = cis‐1,2‐bis(diphenylphosphino)ethene; solv = 0.5THF·2H2O and 2H2O for ax‐CoHS2P2 and eq‐CoHS2P2, respectively), by varying the crystallization temperatures. Despite both diastereoisomers adopting distorted square pyramidal geometries, the bidentate cis‐dppen ligand chelates to the central Co(II) either in an axial‐equatorial or equatorial‐equatorial manner, with a boron‐hydrogen binding to the metal center. Magnetic studies reveal differences in g‐values between these axial‐equatorial isomers. X‐band electron paramagnetic resonance spectra suggest rapid equilibrium and potential conformational interconversion in response to temperature changes in solution. Magnetic measurements indicate field‐induced slow relaxation of magnetization in this low‐spin S = 1/2 system, with spin‐lattice relaxations dominated by Raman and quantum tunneling of magnetization mechanisms due to the absence of thermally populated excited states.

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Temperature‐Driven Axial‐Equatorial Isomerism and Magnetic Relaxation on Low‐Spin Co(II) Borohydride Complexes

Wang,

Li,

Zhang

et al. 2024

Chin. J. Chem.

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Multielectron transfer and field-induced slow magnetic relaxation in opto-electroactive spin crossover cobalt(ii) complexes: structure–function correlations

Rabelo,

Toma,

Julve

et al. 2024

Inorg. Chem. Front.

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Variation in the zero-point energy difference via electrostatic interactions in Co(ii)-Cltpy-based spin-crossover molecular materials

Dutta,

Ghosh

et al. 2025

J. Mater. Chem. C

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How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(ii) complexes

Abstract: A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1–3) and 3 (4); X...

Cited by 5 publications

References 102 publications

Temperature‐Driven Axial‐Equatorial Isomerism and Magnetic Relaxation on Low‐Spin Co(II) Borohydride Complexes

Temperature‐Driven Axial‐Equatorial Isomerism and Magnetic Relaxation on Low‐Spin Co(II) Borohydride Complexes

Multielectron transfer and field-induced slow magnetic relaxation in opto-electroactive spin crossover cobalt(ii) complexes: structure–function correlations

Variation in the zero-point energy difference via electrostatic interactions in Co(ii)-Cltpy-based spin-crossover molecular materials

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