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

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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