Synthesis of Fullerene Derivatives with Novel Structures-Liquid-Phase versus Solid-State Reactions

摘要

Reactions of C_(60) with various carbon nucleophiles,particularly those with substituted acetylide and fluorenide ions in the liquid phase,give various C_(60) derivatives.While the reaction with cyanide salts only affords the cyanated C_(60) in liquid phase,the solid-state mechanochemical reaction selectively gives the dumbbell-shaped dimer.As typically shown by this example,the solid-state reaction was found to be quite advantageous for the formation of various types of fullerene dimers.The reaction of C_(60) with phthalazine also results in formation of entirely different products depending on the reaction phase.While the solid-state reaction gives a fullerene dimer incorporated in a bicyclic framework,the liquid-phase thermal reaction affords a derivative of an open-cage fullerene.Utilizing this reaction,an attempt has been made for organic synthesis of endohedral fullerene encapsulating molecular hydrogen through a series of procedures,i.e.,opening a hole on the fullerene cage,insertion of molecular hydrogen,and reduction of the size of the opening.