Quantifying Magnetic Anisotropy of Series of Five‐Coordinate CoII Ions: Experimental and Theoretical Insights

Stabilizing large easy-axis type magnetic anisotropy in molecular complexes is a challenging task, yet it is crucial for the development of information storage devices and applications in molecular spintronics. Achieving this requires a deep understanding of electronic structure and the relationships between structure and properties to develop magneto-structural correlations that are currently unexplored in the literature. Herein, a series of five-coordinate distorted square pyramidal CoII complexes [Co(L)(X2)].CHCl3 (where X = Cl (1), Br (2), or I (3)) is reported, all exhibiting easy-axis magnetic anicotropy. The size of the zero field splitting axial parameter (D) is quantitatively determined (1 = −72; 2 = −67 and 3 = −25 cm−1) using a cantilever torque magnetometry which is further firmly supported by magnetic susceptibility, and EPR measurements. The study of the magnetization relaxation dynamics reveals field-induced slow relaxation of magnetization due to the predominant Raman relaxation process. Theoretical calculations on 1–3 and optimized model complexes of 1 reveal insights into the electronic structure and highlight the impact of steric and electronic effects on modulating the D values. Overall, the studies reported pave the way for designing a new generation of CoII complexes with enhanced axiality and a lower rhombicity.