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Two air-stable Co(III)–Co(II) mixed-valence complexes of molecular formulas [CoIICoIII(L)(DMAP)3(CH3COO)]·H2O·CH3OH (1) and [CoIICoIII(L)(4-Pyrrol)3 (CH3COO)]·0.5CH2Cl2 (2) (H4L = 1,3-bis-(5-methyl pyrazole-3-carboxamide) propane; DMAP = 4-dimethylaminopyridine; and 4-Pyrrol = 4-pyrrolidinopyridine) were synthesized and characterized by single-crystal X-ray crystallography, high-field electron paramagnetic resonance (HFEPR) spectroscopy, and magnetic measurements. Both complexes possess one five-coordinated paramagnetic Co(II) ion and one six-coordinated Co(III) ion with octahedral geometry. Direct-current magnetic susceptibility and magnetization measurements show the easy-axis magnetic anisotropy that is also confirmed by low-temperature HFEPR measurements and theoretical calculations. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal their field-assisted slow magnetic relaxation, which is a characteristic behavior of single-molecule magnets (SMMs), caused by the individual Co(II) ion. The effective energy barrier of complex 1 (49.2 cm−1) is significantly higher than those of the other dinuclear Co(III)–Co(II) SMMs. This work hence presents the first instance of the dinuclear Co(III)–Co(II) single-molecule magnets with a five-coordinated environment around the Co(II) ion. [ABSTRACT FROM AUTHOR]

Recently, the choice of ligand and geometric control of mononuclear complexes, which can affect the relaxation pathways and blocking temperature, have received wide attention in the field of single-ion magnets (SIMs). To find out the influence of the coordination environment on SIMs, two four-coordinate mononuclear Co(II) complexes [NEt4][Co(PPh3)X3] (X = Cl−, 1; Br−, 2) have been synthesized and studied by X-ray single crystallography, magnetic measurements, high-frequency and -field EPR (HF-EPR) spectroscopy and theoretical calculations. Both complexes are in a cubic space group Pa3¯ (No. 205), containing a slightly distorted tetrahedral moiety with crystallographically imposed C3v symmetry through the [Co(PPh3)X3]− anion. The direct-current (dc) magnetic data and HF-EPR spectroscopy indicated the anisotropic S = 3/2 spin ground states of the Co(II) ions with the easy-plane anisotropy for 1 and 2. Ab initio calculations were performed to confirm the positive magnetic anisotropies of 1 and 2. Frequency- and temperature-dependent alternating-current (ac) magnetic susceptibility measurements revealed slow magnetic relaxation for 1 and 2 at an applied dc field. Finally, the magnetic properties of 1 and 2 were compared to those of other Co(II) complexes with a [CoAB3] moiety. [ABSTRACT FROM AUTHOR]