2020, Krylov, Denis, Velkos, Georgios, Chen, Chia-Hsiang, Büchner, Bernd, Kostanyan, Aram, Greber, Thomas, Avdoshenko, Stanislav M., Popov, Alexey A.

Two isomers of metallofullerene Dy2S@C82 with sulfur-bridged Dy ions exhibit broad magnetic hysteresis with sharp steps at sub-Kelvin temperature. Analysis of the level crossing events for different orientations of a magnetic field showed that even in powder samples, the hysteresis steps caused by quantum tunneling of magnetization can provide precise information on the strength of intramolecular Dy⋯Dy interactions. A comparison of different methods to determine the energy difference between ferromagnetic and antiferromagnetic states showed that sub-Kelvin hysteresis gives the most robust and reliable values. The ground state in Dy2S@C82 has ferromagnetic coupling of Dy magnetic moments, whereas the state with antiferromagnetic coupling in Cs and C3v cage isomers is 10.7 and 5.1 cm-1 higher, respectively. The value for the Cs isomer is among the highest found in metallofullerenes and is considerably larger than that reported in non-fullerene dinuclear molecular magnets. Magnetization relaxation times measured in zero magnetic field at sub-Kelvin temperatures tend to level off near 900 and 3200 s in Cs and C3v isomers. These times correspond to the quantum tunneling relaxation mechanism, in which the whole magnetic moment of the Dy2S@C82 molecule flips at once as a single entity. © the Partner Organisations.

2016, Liu, Fupin, Gao, Cong-Li, Deng, Qingming, Zhu, Xianjun, Kostanyan, Aram, Westerström, Rasmus, Wang, Song, Tan, Yuan-Zhi, Tao, Jun, Xie, Su-Yuan, Popov, Alexey A., Greber, Thomas, Yang, Shangfeng

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.