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Article Dans Une Revue Chemical Science Année : 2023

Magnetic hysteresis and large coercivity in bisbenzimidazole radical-bridged dilanthanide complexes

Résumé

A judicious combination of radical ligands innate to diffuse spin orbitals with paramagnetic metal ions elicits strong magnetic exchange coupling which leads to properties important for future technologies. This metal-radical approach aids in effective magnetic communication of especially lanthanide ions as their 4f orbitals are contracted and not readily accessible. Notably, a high spin density on the donor atoms of the radical is required for strong coupling. Such molecules are extremely rare owing to high reactivity rendering their isolation challenging. Herein, we present two unprecedented series of bisbenzimidazolebased dilanthanide complexes [(Cp*(2)Ln)(2)(mu-Bbim)] (1-Ln = Gd, Tb, Dy, Bbim = 2,2'-bisbenzimidazole) and [K(crypt-222)][(Cp*(2)Ln)(2)(mu-Bbimc)] -(2-Ln = Gd, Tb, Dy), where the latter contains the first Bbim(3)- c radical matched with any paramagnetic metal ion. The magnetic exchange constant for 2-Gd of J = -1.96(2) cm(-1) suggests strong antiferromagnetic Gd-radical coupling, whereas the lanthanides in 1-Gd are essentially uncoupled. Ab initio calculations on 2-Tb and 2-Dy uncovered coupling strengths of -4.8 and -1.8 cm(-1). 1-Dy features open hysteresis loops with a coercive field of Hc of 0.11 T where the single-molecule magnetism can be attributed to the single-ion effect due to lack of coupling. Excitingly, pairing the effective magnetic coupling with the strong magnetic anisotropy of Dy results in magnetic hysteresis with a blocking temperature TB of 5.5 K and coercive field H-C of 0.54 T, ranking 2-Dy as the second best dinuclear single-molecule magnet containing an organic radical bridge. A Bbim(4)- species is formed electrochemically hinting at the accessibility of Bbim-based redox-active materials.

Domaines

Chimie
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Dates et versions

hal-04137851 , version 1 (22-06-2023)

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Paternité - Pas d'utilisation commerciale

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Florian Benner, Léo La Droitte, Olivier Cador, Boris Le Guennic, Selvan Demir. Magnetic hysteresis and large coercivity in bisbenzimidazole radical-bridged dilanthanide complexes. Chemical Science, 2023, 14, pp.5577-5592. ⟨10.1039/d3sc01562a⟩. ⟨hal-04137851⟩
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