A systematic study of the influence of ligand field on the slow magnetic dynamics of Co(ii)-diimine compounds

Abstract

Herein we report heteroleptic Co(II) diimine complexes [Co(H₂bip)₂Cl₂] (1), [Co(H₂bip)₂Br₂] (2), [Co(H₂bip)₃]Br₂·1MeOH (3) and [Co(H₂bip)₂(Me₂bpy)]Br₂·(MeCN)_0.5·(H₂O)_0.25 (4) (H₂bip = 2,2′-bi-1,4,5,6-tetrahydropyrimidine, bpy = 2,2′-dipyridyl, Me₂bpy = 4,4′-Me-2,2′-dipyridyl), purposefully prepared to enable a systematic study of magnetic property changes arising from the increase of overall ligand field from σ/π-donor chlorido (1) to π-acceptor 4,4′Me-2,2′bpy (4). The presence of axial and rhombic anisotropy (D and E) of these compounds is sufficient to allow 1–4 to show field-induced slow relaxation of magnetization. Interestingly, we found as the effective ligand field is increased in the series, rhombicity (E/D) decreases, and the magnetic relaxation profile changes significantly, where relaxation of magnetization at a specific temperature becomes gradually faster. We performed mechanistic analyses of the temperature dependence of magnetic relaxation times considering Orbach relaxation processes, Raman-like relaxation and quantum tunnelling of magnetization (QTM). The effective energy barrier of the Orbach relaxation process (U_eff) is largest in compound 1 (19.2 cm⁻¹) and gradually decreases in the order 1 > 2 > 3 > 4 giving a minimum value in compound 4 (8.3 cm⁻¹), where the Raman-like mechanism showed the possibility of different types of phonon activity below and above ∼2.5 K. As a precursor of 1, the tetrahedral complex [Co(H₂bip)Cl₂] (1a) was also synthesized and structurally and magnetically characterized: this compound exhibits slow relaxation of magnetization under an applied dc field (1800 Oe) with a record slow relaxation time of 3.39 s at 1.8 K.