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Dysprosiacarboranes: A New Type of Organometallic Single-Molecule Magnets

preprint
submitted on 14.10.2019 and posted on 16.10.2019 by Peng-Bo Jin, Yuan-Qi Zhai, Ke-Xin Yu, Richard E. P. Winpenny, Yan-Zhen Zheng
Dicarbollide ion, nido-C2B9H112- is isoelectronic with cyclopentadienyl. Here 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{η25-C6H4(CH2)2C2B9H9}2Li] 3 and show that dicarbollide ligands impose strong magnetic axiality on the central Dy(III) ion. The effective energy barrier (Ueff) for loss of magnetisation can be varied by the substitution pattern on the dicarbollide. This is demonstrated by comparing complexes of nido-C2B9H112- and nido-[o-xylylene-C2B9H9]2- which show Ueff of 430(5) K and 804(7) K, respectively. The blocking temperature defined by the open hysteresis temperature of 3 reaches 6.8 K. Moreover, the linear complex [Dy(C2B9H11)2]- is predicted to have comparable SMM properties with linear [Dy(CpMe3)2]+ complex. As such, carboranyl ligands and its derivatives may open a new type of organometallic ligands for high-performance SMM design.

History

Email Address of Submitting Author

zheng.yanzhen@xjtu.edu.cn

Institution

Xi'an Jiaotong University

Country

CHINA

ORCID For Submitting Author

0000-0003-4056-097X

Declaration of Conflict of Interest

no conflicts of interest

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