What Controls the Sign and Magnitude of Magnetic Anisotropy in Tetrahedral Cobalt(II) Single-Ion Magnets?

Abstract

A family of mononuclear tetrahedral cobalt(II) thiourea complexes, [Co(L₁)₄](NO₃)₂ (1) and [Co(L_x)₄](ClO₄)₂ where x = 2 (2), 3 (3), 4 (4) (where L₁ = thiourea, L₂ = 1,3-dibutylthiourea, L₃ = 1,3-phenylethylthiourea, and L₄ = 1,1,3,3-tetramethylthiourea), has been synthesized using a rationally designed synthetic approach, with the aim of stabilizing an Ising-type magnetic anisotropy (-D). On the basis of direct-current, alternating-current, and hysteresis magnetic measurements and theoretical calculations, we have identified the factors that govern the sign and magnitude of D and ultimately the ability to design a single-ion magnet for a tetrahedral cobalt(II) ion. To better understand the magnetization relaxation dynamics, particularly for complexes 1 and 2, dilution experiments were performed using their diamagnetic analogues, which are characterized by single-crystal X-ray diffraction with the general molecular formulas of [Zn(L₁)₄](NO₃)₂ (5) and [Zn(L₂)₄](ClO₄)₂ (6). Interestingly, intermolecular interactions are shown to play a role in quenching the quantum tunneling of magnetization in zero field, as evidenced in the hysteresis loop of 1. Complex 2 exhibits the largest U_eff value of 62 cm^-1 and reveals open hysteresis loops below 4 K. Furthermore, the influence of the hyperfine interaction on the magnetization relaxation dynamics is witnessed in the hysteresis loops, allowing us to determine the electron/nuclear spin S(Co) = ³/₂/I(Co) = ⁷/₂ hyperfine coupling constant of 550 MHz, a method ideally suited to determine the hyperfine coupling constant of highly anisotropic metal ions stabilized with large D value, which are otherwise hard to determine by conventional methods such as electron paramagnetic resonance.