Template Polymerizations by Using Topochemical Polymerization

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In order to establish the geometrical requirements for the topochemical polymerizations of quinodimethanes, we revealed the relation between polymerizablity in the crystalline state and the crystal structures of a series of the monomers. X-ray crystallographic studies revealed that both the parallel stacking of the quinodimethane rings and the 7.3 A of the stacking distances are requisite for the topochemical polymerizations. This distance corresponds to the repeating unit of the formed polymers. Therefore, we concluded that similarity between the molecular arrangements in the crystalline state and the molecular structures of the formed polymers plays an important role for the topochemical polymerizations. Moreover, we demonstrated that some quinodimethanes provide peroxy crystalline polymers by an alternating copolymerization with molecular oxygen in the crystalline state. The crystal structural analysis illustrated the unique geometry for the reactions with molecular oxygen.On the other hand, we demonstrated novel supramolecular assemblies of seocnday dialkylammonium cations with pybox ligands. They,have orthogonal connections, and should be useful for construction of the well-defined ladder structures as templates for topochemical polymerization for diacetylene compounds.