Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

Fupin Liu; Song Wang; Cong-Li Gao; Qingming Deng; Xianjun Zhu; Aram Kostanyan; Rasmus Westerström; Fei Jin; Su-Yuan Xie; Alexey A Popov; Thomas Greber; Shangfeng Yang

doi:10.1002/anie.201611345

Mononuclear Clusterfullerene Single-Molecule Magnet Containing Strained Fused-Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster

Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1830-1834. doi: 10.1002/anie.201611345. Epub 2017 Jan 12.

Authors

Affiliations

¹ Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, 230026, China.
² State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
³ Leibniz Institute for Solid State and Materials Research Dresden, Helmholtzstrasse 20, Dresden, 01069, Germany.
⁴ Physik-Institut, Universität Zürich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.

Abstract

Fused-pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non-IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused-pentagons, making it difficult to access the single-atom properties. Herein, we report the syntheses and isolations of novel non-IPR mononuclear clusterfullerenes MNC@C₇₆ (M=Tb, Y), in which one pair of strained fused-pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C₇₆ (M=Tb, Y) were determined unambiguously by single-crystal X-ray diffraction, featuring a non-IPR C_2v (19138)-C₇₆ cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR-obeying C₈₂ cages. The TbNC@C₇₆ molecule is found to be a field-induced single-molecule magnet (SMM).

Keywords: clusterfullerenes; cyanide compounds; endohedral fullerenes; non-IPR carbon cage; single-molecule magnets.

Publication types

Research Support, Non-U.S. Gov't

Grants and funding

648295/ERC_/European Research Council/International