Template Polymerizations by Using Topochemical Polymerization

为了建立醌二甲烷类拓扑化学聚合的几何要求，我们揭示了一系列单体的结晶状态下的可聚合性和晶体结构之间的关系。X-射线晶体学研究表明，醌二甲烷环的平行堆积和堆积距离为7.3埃是拓扑化学聚合所必需的。该距离对应于所形成的聚合物的重复单元。因此，我们得出结论，在结晶状态下的分子排列和所形成的聚合物的分子结构之间的相似性起着重要的作用的拓扑化学聚合。此外，我们证明，一些醌二甲烷提供过氧结晶聚合物的交替共聚与分子氧在结晶状态。晶体结构分析表明了与分子氧反应的独特几何构型，另一方面，我们证明了新型的二烷基铵阳离子与pybox配体的超分子组装体。它们具有正交连接，并且应该是有用的，用于构造良好定义的梯形结构作为模板用于二乙炔化合物的拓扑化学聚合。

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.