Tuning Magnetic Anisotropy in Co(II) Tetrahedral Carbazole-Modified Phosphine Oxide Single-Ion Magnets: Importance of Structural Distortion versus Heavy-Ion Effect

Three mononuclear cobalt-(II) tetrahedral complexes [Co-(CzPh2PO)2X2] (CzPh2PO = (9H-carbazol-9-yl)-diphenylphosphine oxide and X = Cl (1), Br (2), I (3)) have been synthesized using a simple synthetic approach to examine their single-ion magnetic (SIM) behavior. A detailed study of the variation in the dynamic magnetic properties of the Co-(II) ion in a tetrahedral ligand field has been carried out by the change of the halide ligand. The axial zero-field splitting parameter D was found to vary from -16.4 cm-1 in 1 to -13.8 cm-1 in 2 and +14.6 cm-1 in 3. All the new complexes exhibit field-induced SIM behavior. The results obtained from ab initio CASSF calculations match well with the experimental data, revealing how halide ions induce a change in the D value as we move from Cl- to I-. The ab initio calculations further reveal that the change in the sign of D is due to the multideterminant characteristics of the ground state wave function of 1 and 2, while single-determinant characteristics are instead observed for 3. To gain a better understanding of the relationship between the structural distortion and the sign and magnitude of D values, magnetostructural D correlations were developed using angular relationships, revealing the importance of structural distortions over the heavy halide effect in controlling the sign of D values. This study broadens the scope of employing electronically and sterically modified phosphine oxide ligands in building new types of air-stable Co-(II) SIMs.