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Issue 9, 2017
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Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism

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Abstract

A method for the selective synthesis of sulfide clusterfullerenes Dy2S@C2n is developed. Addition of methane to the reactive atmosphere reduces the formation of empty fullerenes in the arc-discharge synthesis, whereas the use of Dy2S3 as a source of metal and sulfur affords sulfide clusterfullerenes as the main fullerene products along with smaller amounts of carbide clusterfullerenes. Two isomers of Dy2S@C82 with Cs(6) and C3v(8) cage symmetry, Dy2S@C72-Cs(10528), and a carbide clusterfullerene Dy2C2@C82-Cs(6) were isolated. The molecular structure of both Dy2S@C82 isomers was elucidated by single-crystal X-ray diffraction. SQUID magnetometry demonstrates that all of these clusterfullerenes exhibit hysteresis of magnetization, with Dy2S@C82-C3v(8) being the strongest single molecule magnet in the series. DC- and AC-susceptibility measurements were used to determine magnetization relaxation times in the temperature range from 1.6 K to 70 K. Unprecedented magnetization relaxation dynamics with three consequent Orbach processes and energy barriers of 10.5, 48, and 1232 K are determined for Dy2S@C82-C3v(8). Dy2S@C82-Cs(6) exhibits faster relaxation of magnetization with two barriers of 15.2 and 523 K. Ab initio calculations were used to interpret experimental data and compare the Dy-sulfide clusterfullerenes to other Dy-clusterfullerenes. The smallest and largest barriers are ascribed to the exchange/dipolar barrier and relaxation via crystal-field states, respectively, whereas an intermediate energy barrier of 48 K in Dy2S@C82-C3v(8) is assigned to the local phonon mode, corresponding to the librational motion of the Dy2S cluster inside the carbon cage.

Graphical abstract: Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism

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Publication details

The article was received on 27 May 2017, accepted on 29 Jun 2017 and first published on 30 Jun 2017


Article type: Edge Article
DOI: 10.1039/C7SC02395B
Citation: Chem. Sci., 2017,8, 6451-6465
  • Open access: Creative Commons BY license
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    Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism

    C. Chen, D. S. Krylov, Stanislav M. Avdoshenko, F. Liu, L. Spree, R. Yadav, A. Alvertis, L. Hozoi, K. Nenkov, A. Kostanyan, T. Greber, A. U. B. Wolter and A. A. Popov, Chem. Sci., 2017, 8, 6451
    DOI: 10.1039/C7SC02395B

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