Alcohol-induced decomposition of Olmstead's crystalline Ag(i)–fullerene heteronanostructure yields ‘bucky cubes’

Abstract

Olmstead's crystalline C₆₀-fullerene–Ag(I) organometallic heteronanostructure [C₆₀{AgNO₃}₅] undergoes an apparently irreversible structural rearrangement upon exposure to low molecular weight aliphatic alcohols leading to a uniquely structured formation of well-oriented fullerene nano/microcrystals (‘bucky cubes’). The mechanism of rearrangement represents a supramolecular analogue of topotactic processes more commonly associated with some purely inorganic materials, such as maghemite, where chemical changes can occur with addition or loss of materials. Hence C₆₀{AgNO₃}₅, whose rearrangement occurs at the nano/molecular level (i.e. not atomic scale), undergoes a transformation from a crystalline organometallic complex to well ordered cube-shaped arrays of needle-like fullerene microcrystals which reflect the original cubic crystal morphology and internal structure. Processing of bucky cubes by reduction with hydrazine results in a Ag nanoparticle–C₆₀ crystal nanocomposite with potential for SERS analyses.