Issue 13, 2024

Solvation/desolvation induced reversible distortion change and switching between spin crossover and single molecular magnet behaviour in a cobalt(ii) complex

Abstract

Coexistence and switching between spin-crossover (SCO) and single molecular magnet (SMM) behaviours in one single complex may lead to materials that exhibit bi-stable and stimuli sensitive properties in a wide temperature range and under multiple conditions; unfortunately, the conflict and dilemma in the principle of approaching SCO and SMM molecules make it particularly difficult; at low temperature, low spin (LS) SCO molecules possess highly symmetrical geometry and isotropic spins, which are not suitable for SMM behaviour. Herein, we overcome this issue by using a rationally designed Co(II) mononuclear complex [Co(MeOphterpy)2] (ClO4)2 (1; MeOphterpy = 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine), the magnetic properties of which reversibly respond to desolvation and solvation. The solvated structure reinforced a low distortion of the coordination sphere via hydrogen bonding between ligands and methanol molecules, while in the desolvated structure a methoxy group flipping occurred, increasing the distortion of the coordination sphere and stabilising the HS state at low temperature, which exhibited a field-induced slow magnetic relaxation, resulting in a reversible switching between SCO and SMM properties within one molecule.

Graphical abstract: Solvation/desolvation induced reversible distortion change and switching between spin crossover and single molecular magnet behaviour in a cobalt(ii) complex

Supplementary files

Article information

Article type
Paper
Submitted
24 11 2023
Accepted
19 1 2024
First published
13 2 2024

Dalton Trans., 2024,53, 5861-5870

Solvation/desolvation induced reversible distortion change and switching between spin crossover and single molecular magnet behaviour in a cobalt(II) complex

H. Zenno, Y. Sekine, Z. Zhang and S. Hayami, Dalton Trans., 2024, 53, 5861 DOI: 10.1039/D3DT03936F

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