Analytical Application of Molecular Recognition by Photochemistry of Excited States

合成了与聚醚结合的分子中含有两个菲单元的新化合物。这些化合物会识别处于激发态的分子或离子，当这些试剂被紫外光激发时，在蒽环上发生光二聚反应，形成三个区域异构体。碱土金属离子如钙离子的加入改变了区域异构体的比例。为了解释这一现象，计算了碱土金属离子的络合形成常数。然而，荧光或吸收光谱等光度方法导致了光的二聚化。采用~1H-核磁共振滴定的方法计算生成常数。从生成常数的结果可以看出，在碱土金属离子中，钙离子形成最稳定的络合物。络合时的化学位移变化表明，钙络合物的构象最适合于光二聚反应。合成了一种新的化合物，该化合物含有两个菲单元，通过芳香族羧胺部分连接到聚醚上。含有2-菲类似物的化合物与钙离子有很强的络合能力，在络合时荧光发射显著增加(40倍)，还合成了含有萘乙酰胺单元的新化合物。虽然在萘和酰胺之间插入了亚甲基单元，但萘的激发态已被猝灭，几乎没有观察到发射。这可能是TICT机制和PET(光致电子转移)机制共同作用的结果。该化合物与钙离子的络合作用引起了萘部分的发射，这种发射是由于络合物的形成使TICT猝灭效率降低所致。

New compounds which contain two anthracene units in the molecules combining with polyether were synthesized. These compounds will recognize molecules or ions at the excited state of the anthracene moieties.When these reagents are excited by UV light, the photo dimerization at anthracen rings occurred, and three regio-isomers formed. The ratio of the regio-isomers was changed by the addition of alkaline earth metal ions such as calcium ion. To elucidate this phenomenon, the complex formation constants for alkaline earth metal ions were evaluated. However, photometric method such as fluorescence or absorption spectrometry caused the photo dimerization. H-NMR titration method was adopted to evaluate the formation constants. From the result of formation constants, we found that calcium ion forms the most stable complex in alkaline earth metal ions. The chemical shift change at the complexation shows that the calcium complex takes the most suitable conformation for photo dimerization.A new compound which has two anthracene units linked to polyether via aromatic carboxamide moiety was synthesized. The compound with 2-anthracene analogue has large complexing ability with calcium ion, and shows large increase of fluorescence emission (40 fold) at the complexation.Tne new compounds which have naphthalene acetamide units was also synthesized. Although the methylene units was inserted between naphthalene and amide moietys, the excited state of naphthalene has been quenched and little emission was observed. This fact may be caused by combination of TICT mechanism and PET (photo induced electron transfer) mechanism. The conplexation of this compound with calcium ion induced an emission from naphthalene moiety, and this emission was caused from a decrease of TICT quenching efficiency by the complex formation.