Study on Molecular Recognition through the Inclusion Complex Formation of Helical Polymers

间规聚甲基丙烯酸甲酯(St-PMMA)是一种立体规整的商品塑料，可以将C_(60)、C_(70)等富勒烯包裹在螺旋腔内形成结晶包合物。我们发现，在甲苯中形成的St-PMMA螺旋空腔能够识别被包裹的富勒烯的大小，并根据客体分子的大小灵活地改变其螺旋结构。在St-PMMA优先包埋的基础上，从炭黑中选择性地得到了较高的富勒烯(&gt；C_&lt；76&gt；)。此外，还发现在St-PMMA螺旋空腔中可以包裹多环芳烃，如芘和菲，从而得到了基于排列客体物种的具有独特性质的新型晶体包合物。当以St-PMMA为增溶剂时，C_&lt；60&gt；可溶于极性溶剂，C_&lt；60&gt；以包合物的形式溶解。此外，我们还开发了一种以不同酯基为侧基的高立体规则聚甲基丙烯酸酯的简便合成工艺。

Syndiotactic poly(methyl methacrylate) (st-PMMA), a stereoregular commodity plastic, can encapsulate fullerenes such as C_<60> and C_<70> within its helical cavity to form a crystalline inclusion complex. We found that the st-PMMA helical cavity formed in toluene recognizes the encapsulated fullerene size and changes its helical structure flexibly depending of the size of guest molecules. On the basis of the preferential encapsulation of st-PMMA, higher fullerenes (> C_<76>) were selectively obtained from carbon soot. Moreover, it was found that polycyclic aromatic hydrocarbons such as pyrene and phenanthrene can be encapsulated in the st-PMMA helical cavity, leading to novel crystalline inclusion complexes with unique characteristics based on the arrayed guest species. We also found C_<60> to be soluble in polar solvents when st-PMMA was used as a solubilizing agent ; C_<60> dissolves through inclusion complex formation. Furthermore, we developed a facile synthetic procedure of highly stereoregular polymethacrylates with various ester groups as pendants.