Magnetic Anisotropy and Relaxation in Four-Coordinate Cobalt(II) Single-Ion Magnets with a [coiio4] Core

A mononuclear four-coordinate Co(II) complex with a [(CoO4)-O-II] core, namely, PPN[Li(MeOH)(4)][Co(L)(2)] (1) (PPN = bis(phosphoranediyl)iminium; H2L = perfluoropinacol), has been studied by X-ray crystallography, magnetic characterization, and theoretical calculations. This complex presents a severely distorted coordination geometry. The O-Co-O bite angle is 83.42 degrees/83.65 degrees, and the dihedral twist angle between the O-Co-O chelate planes is 55.6 degrees. The structural distortion results in a large easy-axis magnetic anisotropy with D = -104(1) cm(-1) and a transverse component with |E| = +4(2) cm(-1). Alternating current (ac) susceptibility measurements demonstrate that 1 exhibits slow relaxation of magnetization at zero static field. However, the frequency-dependent out-of-phase (chi"(M)) susceptibilities of 1 at 0 Oe do not show a characteristic maximum. Upon the application of a dc field or the dilution with a diamagnetic Zn matrix, the quantum tunneling of magnetization (QTM) process can be successfully suppressed. Notably, after dilution with the Zn matrix, the obtained sample exhibits a structure different from that of the pristine complex. In this altered sample, the asymmetric unit does not contain the Li(MeOH)(4)(+) cation, resulting in an O-Co-O bite angle of 86.05 degrees and a dihedral twist angle of 75.84 degrees, thereby leading to an approximate D-2d symmetry. Although such differences are not desirable for magnetic studies, this study still gives some insights. Theoretical calculations reveal that the D parameter is governed by the O-Co-O bite angle, in line with our previous report for other tetrahedral Co(II) complex with a [(CoN4)-N-II] core. On the other hand, the rhombic component is found to increase as the dihedral angle deviates from 90 degrees. These findings provide valuable guidelines for fine-tuning the magnetic properties of Co(II) complexes.