Crystalline functionalized endohedral C60 metallofullerides

Ayano Nakagawa, Makiko Nishino, Hiroyuki Niwa, Katsuma Ishino, Zhiyong Wang, Haruka Omachi, Ko Furukawa, Takahisa Yamaguchi, Tatsuhisa Kato, Shunji Bandow, Jeremy Rio, Chris Ewels (), Shinobu Aoyagi and Hisanori Shinohara ()
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Ayano Nakagawa: Nagoya University
Makiko Nishino: Nagoya University
Hiroyuki Niwa: Nagoya University
Katsuma Ishino: Nagoya University
Zhiyong Wang: Nagoya University
Haruka Omachi: Nagoya University
Ko Furukawa: Niigata University
Takahisa Yamaguchi: Kyoto University
Tatsuhisa Kato: Kyoto University
Shunji Bandow: Meijo University
Jeremy Rio: CNRS UMR6502
Chris Ewels: CNRS UMR6502
Shinobu Aoyagi: Nagoya City University
Hisanori Shinohara: Nagoya University

Nature Communications, 2018, vol. 9, issue 1, 1-9

Abstract: Abstract Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C60 such as (metal)@C82, and there are no reported purified C60-based monomeric metallofullerenes, except for [Li@C60]+(SbCl6)− salt. Pure (metal)@C60 compounds have not been obtained because of their extremely high chemical reactivity. One route to their stabilization is through chemical functionalization. Here we report the isolation, structural determination and electromagnetic properties of functionalized crystalline C60-based metallofullerenes Gd@C60(CF3)5 and La@C60(CF3)5. Synchrotron X-ray single-crystal diffraction reveals that La and Gd atoms are indeed encapsulated in the Ih-C60 fullerene. The HOMO-LUMO gaps of Gd@C60 and La@C60 are significantly widened by an order of magnitude with addition of CF3 groups. Magnetic measurements show the presence of a weak antiferromagnetic coupling in Gd@C60(CF3)3 crystals at low temperatures.

Date: 2018
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DOI: 10.1038/s41467-018-05496-8

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