Dysprosiacarboranes as Organometallic Single-Molecule Magnets |
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| Authors: | Peng-Bo Jin Yuan-Qi Zhai Ke-Xin Yu Prof?Dr Richard E P Winpenny Prof?Dr Yan-Zhen Zheng |
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| Institution: | 1. Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory of Mechanical Behavior, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Mater, Xi'an Key Laboratory of Sustainable Energy and Materials Chemistry and School of Science, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, 710054 P. R. China;2. Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL UK |
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| Abstract: | The dicarbollide ion, nido-C2B9H112? is isoelectronic with cyclopentadienyl. Herein, we make dysprosiacarboranes, namely (C2B9H11)2Ln(THF)2]Na(THF)5] (Ln=Dy, 1Dy ) and (THF)3(μ-H)3Li]2{η5-C6H4(CH2)2C2B9H9}Dy{η2:η5-C6H4(CH2)2C2B9H9}2Li] 3Dy and show that dicarbollide ligands impose strong magnetic axiality on the central DyIII ion. The effective energy barrier (Ueff) for the loss of magnetization can be varied by the substitution pattern on the dicarbollide. This finding is demonstrated by comparing complexes of nido-C2B9H112? and nido-o-xylylene-C2B9H9]2?, which show a Ueff of 430(5) K and 804(7) K, respectively. The blocking temperature defined by the open hysteresis temperature of 3Dy reaches 6.8 K. Moreover, the linear complex Dy(C2B9H11)2]? is predicted to have comparable properties with the linear Dy(CpMe3)2]+ complex. As such, carboranyl ligands and their derivatives may provide a new type of organometallic ligand for high-performance single-molecule magnets. |
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| Keywords: | carboranes cyclopentadienyl ligands dysprosium energy barriers magnetic properties |
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