Molecular Discrimination in the Excited States and Its Synthetic Applications

本文对激发态分子识别及其合成应用进行了研究，得到了以下结果：在激发态下具有两个发色团的有机分子的分子内相互作用的研究，为激态下的单峰和三峰的结构和性质提供了重要的信息。具有l-氰萘发色团和烯烃或呋喃发色团的有机分子的分子内光环加成以立体选择的方式得到（2+2）或（4+4）环加合物。考察了添加剂和溶剂的影响。此外，含烯基的萘酸甲酯衍生物通过分子内1,10-氢的萃取得到了一种新的8元酮。手性1,4-二氰萘衍生物和2,2′-二甲基-1,1′-二氰萘基被某些手性猝灭剂猝灭时，观察到荧光的手性分辨。在异构体淬火中也观察到手性歧视。9,10-二氰蒽以立体选择性的方式将醇通过苯的络合物与芳烯的分子间和分子内光加成增敏。在手性1,4-二氨基萘衍生物或1,4-二氨基萘存在下，甲醇与手性或非手性芳烯的光加成以对映或非对映方式发生。

The molecular discrimination in the excited states and its synthetic applications have been studied and the following results were obtained.1. The studies on the intramolecular interaction of organic molecules having two chromophores in the excited states provide significant information regarding the structures and the properties of exciplexes and triplexes in the exciteds states.2. The intramolecular photocycloaddition of organic molecules having l-cyanonaphthalene chromophore and alkenes or furan chromophore gives (2+2) or (4+4) cycloadducts in a stereoselective manner. The additive and solvent effects are also investigated. In addition, the photoreaction of methyl naphthoate derivatives bearing alkenyl groups gives a novel 8-membered ketone via intramolecular 1,10-hydrogen abstraction.3. Chiral discrimination is observed in the fluorescence quenching of chiral 1,4-dicyanonaphthalene derivatives and 2,2' -dimethyl-1,1' -bianthryl by some chiral quenchers. Chiral discrimination is also observed in the exciplex quenching.4. Inter-and intramolecular photoaddition of alcohols to arylalkenes via exciplexes in benzene is sensitized by 9,10-dicyanoanthracene in a stereoselective manner. The photoaddition of methanol to chiral or achiral arylalkenes in the presence of chiral 1,4-dicyanonaphthalene derivatives or 1,4-dicyanonaphthalene occurs in an enantio-or diastereoselective manner.