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Triangular Monometallic Cyanide Cluster Entrapped in Carbon Cage with Geometry-Dependent Molecular Magnetism
Fupin Liu1, Cong-Li Gao2, Qingming Deng3
1Hefei National Laboratory for Physical Sciences at Microscale, Key Laboratory of Materials for Energy Conversion, Chinese Academy of Sciences, Department of Materials Science and Engineering, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China (USTC) , Hefei 230026, China.
None:
Clusterfullerenes are capable of entrapping a variety of metal clusters within carbon cage, for which the entrapped metal cluster generally keeps its geometric structure (e.g., bond distance and angle) upon changing the isomeric structure of fullerene cage, and whether the properties of the entrapped metal cluster is geometry-dependent remains unclear. Herein we report an unusual triangular monometallic cluster entrapped in fullerene cage by isolating several novel terbium cyanide clusterfullerenes (TbNC@C82) with different cage isomeric structures. Upon varying the isomeric structure of C82 cage from C2(5) to Cs(6) and to C2v(9), the entrapped triangular TbNC cluster exhibits significant distortions as evidenced by the changes of Tb-C(N) and C-N bond distances and variation of the Tb-C(N)-N(C) angle by up to 20°, revealing that the geometric structure of the entrapped triangular TbNC cluster is variable. All three TbNC@C82 molecules are found to be single-ion magnets, and the change of the geometric structure of TbNC cluster directly leads to the alternation of the magnetic relaxation time of the corresponding TbNC@C82 clusterfullerene.
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