Field-induced single ion magnet behaviour of discrete and one-dimensional complexes containing [bis(1-methylimidazol-2-yl)ketone]-cobalt(II) building units

Abstract

We describe herein the first examples of six-coordinate Co^II single-ion magnets (SIMs) based on the β-diimine ^Mebik ligand [^Mebik = bis(1-methylimidazol-2-yl)ketone]: two mononuclear [Co^II(^Rbik)₂L₂] complexes and one mixed-valence {CoIII2Co^II}_n chain of formulas [Co^II(^Mebik)(H₂O)(dmso)(μ-NC)₂CoIII2(μ-2,5-dpp)(CN)₆]_n·1.4nH₂O (3) [L = NCS (1), NCSe (2) and 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine (3)]. Two bidentate ^Mebik molecules plus two monodentate N-coordinated pseudohalide groups in cis positions build somewhat distorted octahedral surroundings around the high-spin cobalt(II) ions in 1 and 2. The diamagnetic [CoIII2(μ-2,5-dpp)(CN)₈]^2- metalloligand coordinates the paramagnetic [Co^II(^Mebik)(H₂O)(dmso)]²⁺ complex cations in a bis-monodentate fashion to afford neutral zigzag heterobimetallic chains in 3. Ab initio calculations, and cryomagnetic dc (2.0-300 K) and ac (2.0-12 K) measurements as well as EPR spectroscopy for 1-3 show the existence of magnetically isolated high-spin cobalt(II) ions with D values of 59.84-89.90 (1), 66.32-93.90 (2) and 70.40-127.20 cm^-1 (3) and field-induced slow relaxation of the magnetization, being thus new examples of SIMs with transversal magnetic anisotropy. The analysis of their relaxation dynamics reveals that the relaxation of the magnetization occurs by the Raman (with values of the n parameter covering the range 6.0-6.8) and direct spin-phonon processes.