Diffusionless solid state reactions in C60 and its supramolecular derivatives: photopolymerization and host–guest cycloaddition

Solid state cycloadditions were carried out in pure C60 and in its clathrate crystals. A novel large-scale photopolymerization method of C60 made it possible to determine the crystal structure of the fullerene photopolymer and isolate its soluble oligomer components. The polymer and the dimer have disordered f.c.c. structures. The polymer consists of a crystalline mixture of various planar oligomers formed in the close packed (1 0 0) and (1 1 1) planes of C60. In photopolymers the number of bonded neighbors is around 2. In C60–1,3-pentadiene clathrate on site cycloaddition takes place between the host and guest molecules. The topochemical conditions in this supramolecular system enhance the formation of an isomer-free cycloadduct with 100% yield.