Template Polymerizations by Using Topochemical Polymerization

为了建立喹二甲烷拓扑化学聚合的几何要求，我们揭示了一系列单体在结晶状态下的可聚合性与晶体结构之间的关系。x射线晶体学研究表明，喹诺二甲烷环的平行堆叠和7.3 A的堆叠距离是拓扑化学聚合的必要条件。这个距离对应于形成的聚合物的重复单元。因此，我们得出结论，晶体状态下的分子排列与形成的聚合物分子结构之间的相似性对拓扑化学聚合起着重要的作用。此外，我们证明了一些喹二甲烷通过与分子氧在结晶状态下的交替共聚提供过氧结晶聚合物。晶体结构分析说明了与分子氧反应的独特几何形状。另一方面，我们展示了具有pybox配体的第二烷基铵阳离子的新型超分子组装。它们具有正交连接，可用于构建定义良好的阶梯结构，作为二乙炔化合物拓扑化学聚合的模板。

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.