LAUSR

Herein, we report two mononuclear dysprosium complexes [Dy(H4L){B(OMe)2(Ph)2}2](Cl)·MeOH (1) and [Dy(H4L){MeOH)2(NCS)2}](Cl) (2) [where H4L = 2,2'-(pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(N-phenylhydrazinecarboxamide)] with different axial coordination environments. The structural analysis revealed that the pentadentate H4L ligand binds through the equatorial position in both complexes. In complex 1, the axial positions are occupied by bidentate dimethoxydiphenyleborate [B(OMe)2(Ph)2]-. On the other hand, in complex 2, one axial position is occupied by two NCS- and one MeOH molecule while another MeOH molecule is coordinated to the other axial position. Magnetic measurements disclose the presence of field-induced slow relaxation of magnetization with an energy barrier of Ueff = 30 K for 1 whereas no such effective barrier was observed in complex 2. Detailed analysis of field and temperature dependence of the relaxation time confirms the major role of Raman, QTM, and direct processes rather than the Orbach process in complex 1. It was observed that [B(OMe)2(Ph)2]- provides higher axial anisotropy which slows down the QTM process (relaxation time for the QTM process is 2.70 × 10-5 s) in 1 as compared to NCS anions and MeOH molecules in 2 (1.03 × 10-8 s), and is responsible for the absence of an effective energy barrier in the latter complex as confirmed by ab initio calculations. The calculations also show that the presence of a large bidentate dimethoxydiphenyleborate ligand in axial positions may result in high-performance Dy-based single-ion magnets.