Tuning the Equatorial Negative Charge in Hexagonal Bipyramidal Dysprosium(III) Single-Ion Magnets to Improve the
Xingwei Cai1, Zhijie Cheng1, Yingying Wu2
1School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, P. R. China.
Abstract:
Taking advantage of the pentaethylene glycol (EO5) and deprotonation of EO5, a family of new structurally hexagonal bipyramidal Dy(III) complexes, [Dy(EO5)(2,6-dichloro-4-nitro-PhO)2](2,6-dichloro-4-nitro-PhO) (1), [Dy(EO5-BPh2)(2,6-dichloro-4-nitro-PhO)2] (2), and [Dy(EO5-BPh2)(2,6-dichloro-4-nitro-PhO)Cl] (3), were controbllably synthesized and structurally characterized. Magnetic measurements show that complex 1 is a zero-field SIM and has an observable hysteresis opening up to 4 K. Conversely, only under extra magnetic field is slow magnetic relaxation observed in 2 and 3. This considerable difference in the magnetic behavior is mainly caused by the change of the equatorial negative charge. Detailed ab initio calculations further elucidate that the quantum tunneling is induced by the presence of equatorial negative charge, and the magnetic anisotropy depends on the axial ligands. This work demonstrates that the absence of the equatorial negative charge should also be considered in the rational design of promising single molecular magnets based on the oblate ions.
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