論文

査読有り
2011年6月

Gd-2@C79N: Isolation, Characterization, and Monoadduct Formation of a Very Stable Heterofullerene with a Magnetic Spin State of S=15/2

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
  • Wujun Fu
  • Jianyuan Zhang
  • Tim Fuhrer
  • Hunter Champion
  • Ko Furukawa
  • Tatsuhisa Kato
  • James E. Mahaney
  • Brian G. Burke
  • Keith A. Williams
  • Kenneth Walker
  • Caitlyn Dixon
  • Jiechao Ge
  • Chunying Shu
  • Kim Harich
  • Harry C. Dorn
  • 全て表示

133
25
開始ページ
9741
終了ページ
9750
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/ja202011u
出版者・発行元
AMER CHEMICAL SOC

The dimetallic endohedral heterofullerene (EHF), Gd-2@C79N, was prepared and isolated in a relatively high yield when compared with the earlier reported heterofullerene, Y-2@C79N. Computational (DFT), chemical reactivity, Raman, and electrochemical studies all suggest that the purified Gd-2@C79N, with the heterofullerene cage, (C79N)(5-) has comparable stability with other better known iso electronic metallofullerene (C-80)(6-) cage species (e.g., Gd3N@C-80). These results describe an exceptionally stable paramagnetic molecule with low chemical reactivity with the unpaired electron spin density localized on the internal diatomic gadolinium cluster and not on the heterofullerene cage. EPR studies confirm that the spin state of Gd-2@C79N is characterized by a half-integer spin quantum number of S = 15/2. The spin (S =1/2) on the N atom of the fullerene cage and two octet spins (S = 7/2) of two encapsulated gadoliniums are coupled with each other in a ferromagnetic manner with a small zero-field splitting parameter D. Because the central line of Gd-2@C79N is due to the Kramer's doublet with a half-integer spin quantum number of S = 15/2, this relatively sharp line is prominent and the anisotropic nature of the line is weak. Interestingly, in contrast with most Gd3+ ion environments, the central EPR line (g = 1.978) is observable even at room temperature in a toluene solution. Finally, we report the first EHF derivative, a diethyl bromomalonate monoadduct of Gd-2@C79N, which was prepared and isolated via a modified Bingel-Hirsch reaction.

リンク情報
DOI
https://doi.org/10.1021/ja202011u
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000292439700031&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/ja202011u
  • ISSN : 0002-7863
  • Web of Science ID : WOS:000292439700031

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