Journal
JOURNAL OF SOLID STATE CHEMISTRY
Volume 299, Issue -, Pages -Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2021.122209
Keywords
Co(II) ion; Magnetic anisotropy; Zero-field; Slow magnetic relaxation
Funding
- Nantong University Analytical Testing Center
- National Natural Science Foundation of China [21776140]
- Science and Technology Projects Fund of Nantong City [JC2020134, JC2020133]
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By synthesizing a mononuclear tetrahedral Co(II) complex, this study demonstrates the method of modulating the coordination environment by varying substitution on the ligand. Magnetic studies reveal that the acute N-Co-N bite angle can influence the magnetic anisotropy of tetrahedral Co(II) complexes.
By modulating the substitution on the oxamide ligand, a mononuclear tetrahedral Co(II) complex (HNEt3)(2)[CoL2] (1) (H2L = N,N'-bis(methanesulfonyl)oxamide) with subtle variation in the CoN4 coordination environment was successfully synthesized, which displays zero-field slow magnetic relaxation and a hysteresis loop at 1.8 K. The complex adopts distorted tetrahedral coordination geometries with acute N-Co-N bite angle imposed by two mutually perpendicular oxamide ligands. Magnetic studies and computational results reveal that the acute N-Co-N bite angle seems to govern the overall magnetic anisotropy of tetrahedral Co(II) complexes with two bidentate chelated ligands containing N-4-donor set. Upon reducing the bite angle, the D parameter increases gradually and reaches the maximum at about 81 degrees, and then show a significant decrease as the angle continuing to decline. This research demonstrates that the easy-axial magnetic anisotropy can be maximized by reducing the bite angle to a certain extent, which is also feasible for tetrahedral cases with other donor sets.
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