Impact of Ligand Substituents on the Magnetization Dynamics of Mononuclear DyIII Single-Molecule Magnets
Mengmeng Wang1, Ying Guo2, Zongsu Han1
1Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071, China.
Abstract:
Two mononuclear DyIII single-molecule magnets with different ligand substituents located far from the coordinating atoms, [Dy(L-NO2)(NO3)] (1) and [Dy(L-Me)(NO3)] (2), and their diamagnetic-ion diluted analogues, 1' and 2', were structurally and magnetically characterized. 1 and 2 have nearly identical coordination environments of DyIII ions with D2d symmetry but different magnetization dynamics. No Orbach process was observed for 1 and 1' in the testing temperature and frequency range, but effective energy barriers of 575 and 829 K for 2 and 2' were obtained, respectively. The opened hysteresis loops were observed until 6 K for 1 and 10 K for 2. Ab initio calculations reveal that the energy gaps between ground and low-lying excited states of 2 are higher than those of 1 and the relaxation rate through quantum tunneling of magnetization of 2 is lower than that of 1 due to the electronic effect of the axial coordinating oxygen atoms influenced by ligand substitutions.
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