Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation

Sho-ichi Iwamatsu; Shizuaki Murata

doi:10.1055/s-2005-872238

ACCOUNT

Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation

Sho-ichi Iwamatsu*, Shizuaki Murata
Graduate School of Environmental Studies, Nagoya University, Chikusa, Nagoya 464-8601, Japan
Fax: +81(52)7894765; e-Mail: iwmt@urban.env.nagoya-u.ac.jp;

Abstract

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Abstract

The carbon-carbon bond scission of the fullerene cage offers an open-cage fullerene derivative having an opening on the fullerene surface. This account summarizes our recent studies on the syntheses of open-cage C₆₀ derivatives as well as their properties of molecular encapsulation. The photochemical rearrangement of the cyclohexadiene derivative of C₆₀ gives bis(fulleroid), the precursor for the cage scission. The photooxygenative carbon-carbon bond cleavage of bis(fulleroid) affords an open-cage diketone derivative having a 12-membered ring. The reaction of the diketone derivative with aromatic hydrazine or hydrazone allows the ring expansion of the orifice by regioselective cage scission to yield a product bearing a 16-membered ring. The orifice in the product is large enough to pass a hydrogen molecule, producing an endohedral hydrogen complex. In the case of the reaction with ortho-phenylenediamine, two carbon-carbon bonds are sequentially cleaved to afford a product having a 20-membered ring orifice. This product spontaneously encapsulates one water molecule to form an endohedral water complex.

1 Introduction
2 Preparation of Open-Cage Fullerenes
2.1 Bis(fulleroid) Derivatives
2.2 Open-Cage Diketone Derivative of C₆₀
2.3 Expansion of the Orifice of the Open-Cage Diketone C₆₀ (1) The Reactions with Aromatic Hydrazines or Hydrazones
2.4 Expansion of the Orifice of the Open-Cage Diketone C₆₀ (2) The Reactions with Aromatic 1,2-Diamines
2.5 Expansion of the Orifice of the Open-Cage Ketolactam C₆₀
3 Molecular Structures of the Open-Cage C₆₀ Derivatives
4 Molecular Encapsulations in the Open-Cage C₆₀ Derivatives
4.1 Hydrogen (H₂)
4.2 Water
5 Conclusion and Future Aspects

Key words

fullerenes - cleavage - ring expansion - host-guest

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Referenzen

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