ja6b09329_si_002.cif (567.74 kB)
Triangular Monometallic Cyanide Cluster Entrapped in Carbon Cage with Geometry-Dependent Molecular Magnetism
dataset
posted on 2016-10-18, 00:00 authored by Fupin Liu, Cong-Li Gao, Qingming Deng, Xianjun Zhu, Aram Kostanyan, Rasmus Westerström, Song Wang, Yuan-Zhi Tan, Jun Tao, Su-Yuan Xie, Alexey A. Popov, Thomas Greber, Shangfeng YangClusterfullerenes
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.