Synthesis of [59]fullerenones through peroxide-mediated stepwise cleavage of fullerene skeleton bonds and X-ray structures of their water-encapsulated open-cage complexes

Zuo Xiao, Jiayao Yao, Dazhi Yang, Fudong Wang, Shaohua Huang, Liangbing Gan, Zhenshan Jia, Zhongping Jiang, Xiaobing Yang, Bo Zheng, Gu Yuan, Shiwei Zhang, Zheming Wang

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Abstract

Fullerene skeleton modification has been investigated through selective cleavage of the fullerene carbon-carbon bonds under mild conditions. Several cage-opened fullerene derivatives including three [59]fullerenones with an 18-membered-ring orifice and one [59]fullerenone with a 19-membered-ring orifice have been prepared starting from the fullerene mixed peroxide 1, C 60(OOtBu)6. The prepositioned tert-butyl peroxy groups in 1 serve as excellent oxygen sources for formation of hydroxyl and carbonyl groups. The cage-opening reactions were initiated by photoinduced homolysis of the tBu-O bond, followed by sequential ring expansion steps. A key step of the ring expansion reactions is the oxidation of adjacent fullerene hydroxyl and amino groups by diacetoxyliodobenzene (DIB). Aminolysis of a cage-opened fullerene derivative containing an anhydride moiety resulted in multiple bond cleavage in one step. A domino mechanism was proposed for this reaction. Decarboxylation led to elimination of one carbon atom from the C 60 cage and formation of [59]fullerenones. The cage-opened [59]fullerenones were found to encapsulate water under mild conditions. All compounds were characterized by spectroscopic data. Single-crystal structures were also obtained for five skeleton-modified derivatives including two water-encapsulated fulleroids.

Original languageEnglish (US)
Pages (from-to)16149-16162
Number of pages14
JournalJournal of the American Chemical Society
Volume129
Issue number51
DOIs
StatePublished - Dec 26 2007

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Fullerenes
Peroxides
Skeleton
X-Rays
X rays
Water
Carbon
Orifices
Derivatives
Hydroxyl Radical
Decarboxylation
Anhydrides
Crystal structure
Single crystals
Oxygen
Atoms
Oxidation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Synthesis of [59]fullerenones through peroxide-mediated stepwise cleavage of fullerene skeleton bonds and X-ray structures of their water-encapsulated open-cage complexes. / Xiao, Zuo; Yao, Jiayao; Yang, Dazhi; Wang, Fudong; Huang, Shaohua; Gan, Liangbing; Jia, Zhenshan; Jiang, Zhongping; Yang, Xiaobing; Zheng, Bo; Yuan, Gu; Zhang, Shiwei; Wang, Zheming.

In: Journal of the American Chemical Society, Vol. 129, No. 51, 26.12.2007, p. 16149-16162.

Research output: Contribution to journalArticle

Xiao, Zuo ; Yao, Jiayao ; Yang, Dazhi ; Wang, Fudong ; Huang, Shaohua ; Gan, Liangbing ; Jia, Zhenshan ; Jiang, Zhongping ; Yang, Xiaobing ; Zheng, Bo ; Yuan, Gu ; Zhang, Shiwei ; Wang, Zheming. / Synthesis of [59]fullerenones through peroxide-mediated stepwise cleavage of fullerene skeleton bonds and X-ray structures of their water-encapsulated open-cage complexes. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 51. pp. 16149-16162.
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abstract = "Fullerene skeleton modification has been investigated through selective cleavage of the fullerene carbon-carbon bonds under mild conditions. Several cage-opened fullerene derivatives including three [59]fullerenones with an 18-membered-ring orifice and one [59]fullerenone with a 19-membered-ring orifice have been prepared starting from the fullerene mixed peroxide 1, C 60(OOtBu)6. The prepositioned tert-butyl peroxy groups in 1 serve as excellent oxygen sources for formation of hydroxyl and carbonyl groups. The cage-opening reactions were initiated by photoinduced homolysis of the tBu-O bond, followed by sequential ring expansion steps. A key step of the ring expansion reactions is the oxidation of adjacent fullerene hydroxyl and amino groups by diacetoxyliodobenzene (DIB). Aminolysis of a cage-opened fullerene derivative containing an anhydride moiety resulted in multiple bond cleavage in one step. A domino mechanism was proposed for this reaction. Decarboxylation led to elimination of one carbon atom from the C 60 cage and formation of [59]fullerenones. The cage-opened [59]fullerenones were found to encapsulate water under mild conditions. All compounds were characterized by spectroscopic data. Single-crystal structures were also obtained for five skeleton-modified derivatives including two water-encapsulated fulleroids.",
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