PREPARARION OF POLYMERS OF CONTROLLED SECONDARY STRUCTURES HAVING FUNCTIONAL GROUP IN THE SIDE CHAINS AND THEIR APPLICATION AS PHOTON/ELECTRON TRANSPORT DEVICES

以L-谷氨酸为原料，通过侧链羧基的酰胺化反应合成了具有侧链基团和1-(1-萘基)乙基的聚(L-谷氨酰胺)L。在溶液中证实了侧链酰胺基团之间的氢键作用，也证实了这些侧链酰胺基团之间的定向和激发能传递，以及它们之间的激发能传递，显示了这些聚合物作为能量传递分子器件的潜在用途。在聚(L-谷氨酸)的侧链中还引入了邻菲罗啉的侧链基团，它与一种合适的Ru化合物络合，使聚合物与类似于Ru的三联吡啶的络合物。邻菲咯啉基团也被转化为三亚甲基桥联紫精类电子受体。合成了含二茂铁基的聚(L-谷氨酰胺)S。这些聚合物的生色团取向、氧化还原活性和光诱导电子转移均表现为t…。此外，这些聚合物还可用作电子传输分子器件。等规聚甲基丙烯酸的侧链中还引入了萘基和吡喃基。证实了侧链酰胺基团之间由于氢键作用而形成的螺旋二级结构，这使得萘基和吡喃基之间可以很容易地进行激发能量转移。通过外加猝灭剂在不同溶剂中的猝灭实验，考察了萘基之间的激发能传递及其与聚合物二级结构的关系。氢键结构的激发能迁移效率是无规结构的1.6倍，这表明等规聚甲基丙烯酰胺S可用作激发能，并可能像聚L-谷氨酰胺一样作为电子传递分子装置。圆二色谱与实验观察的结果一致，表明生色团间的相互作用与聚合物的二级结构之间存在联系。较少

Poly(L-glutamine)s having side-chain pyrenyl and 1-(1-naphthyl)ethyl groups were prepared by amidation of the side-chain carboxyl groups of poly(L-glutamic acid). Hydrogen bonding among the side-chain amide groups was confirmed in solution, and orientation of the pyrenyl groups and excitation energy transport among them as well as excitation energy transfer between the naphthyl and pyrenyl groups were also confirmed, showing the potential use of these polymers as energy-transporting molecular devices. Pendant phenanthroline groups were also introduced in the side chains of poly(L-glutamic acid), whose complexation with an appropriate ruthenium compound affored polymers with complexes similar to ruthenium trisbipyridyl. The phenanthroline groups were also converted to trimethylene-bridged viologen-like electron acceptors. Poly(L-glutamine)s with ferrocenyl groups were also prepared. The chromophore orientation, redox activity, and photo-induced electron transfer of these polymers show t … More hat these polymers are useful as electron-transporting molecular devices.Naphthyl and pyrenyl groups were also introduced in the side chains of isotactic poly(methacrylic acid). The helical seondary structure induced by hydrogen bonding among the side-chain amide groups were confirmed, which allows a facile excitation energy transfer between the naphthyl and pyrenyl groups. Excitation energy transport among the naphthyl groups and its dependence on the polymer secondary structure were examined by quenching experments in various solvents using an externally-added quencher. The hydrogen-bonded structure was found to afford excitation energy migration ca. 1.6 times as efficient as that in the random-colied structure, showing these isotactic poly(methacrylamide)s are useful as excitation energy and possibly electron-transporting molecular devices as with poly(L-glutamine)s.Agreement between the circular dichroism, theoretically calculated based on the polymer structures obtained by molecular mechanics calculations, and that experimentally observed supports the estimated secondary structure, showing the relationship between the inter-chromophore interaction and the polymer secondary structure. Less