Synthesis and Physical Properties of Novel Cationic Disk-shaped Molecules

盘状多环芳烃“冠烯”是最引人注目的分子之一，其结构特征在柱状液晶、有机晶体管、电致发光显示器、有机太阳能电池等有机光电子材料和器件中具有广阔的应用前景。冠烯的苯环被杂环取代有望改变它们的电子和结构性质。到目前为止，已报道了一些杂冠烯(或杂环烯)，包括噻吩环、呋喃环或哒嗪环。本研究发现了一种新型的光诱导偶氮冠烯分子内Diels-Alder型反应合成偶氮冠烯的方法。用9-(2-萘基乙烯基)-2-硫代喹啉盐的乙腈溶液辐射得到偶氮冠烯，产率为80%的…更多的是通过分子内的Diels-Alder类型的反应，然后是氧化-光环化。2-(3-硫苯基)-萘并[1，2-a]喹啉的光反应也得到了偶氮冠烯，产率为82%。应用这一新反应，我们尝试合成了具有两个四元氮原子的2a，8a-重氮冠烯。2，8-二甲基喹啉与3-硫代苯甲醛和吡啶-4-甲醛分步缩合得到不对称的二烯烃。二烯烃的光反应生成2a，8a-重氮冠烯，产率为5%，副产物为吡啶酮型。该反应还得到了双冠烯的重氮化衍生物，偶氮冠烯在稀溶液中表现出很强的发光。然而，UV/Vis、荧光和核磁共振滴定研究证实，随着溶剂浓度或极性的增加，荧光光谱向长波方向移动，量子产率降低。我们还发现，偶氮冠烯-聚阴离子络合物，如与阴离子聚合物的聚离子络合物或插层无机材料，其荧光性质与聚阴离子基质有关，而且聚离子络合物的阳离子交换比也会影响其光学性质。较少

The disk-shaped polycyclic aromatic hydrocarbon, "coronene", is a one of the most fascinating molecules, and whose structural feature shows promising application for organic photo-electron materials and devices such as columnar liquid crystals, organic transistors, electro-luminescence displays, and organic solar cells. Replacement of the benzene ring of coronene by a heterocycle would be expected to change their electronic and structural properties. Some heterocoronenes (or heterocirculenes), including thiophene, furan, or pyridazine rings have been reported until now. However, azonia derivative of coronene, in which a bridehead carbon atom replaced by quaternary nitrogen atom, was still unknown.In this study, we have discovered an efficient synthesis of azoniacoronene by novel photo-induced intra-molecular Diels-Alder type reaction of azoniathia[6]helicenes. Irradiation to an acetonitrile solution of, 9-(2-naphthylvinyl)-thieno- quinolizinium salt gave the azoniacoronene in 80% yield … More by the intra-molecular photo-Diels-Alder type reaction followed by the oxidative-photocyclization. Photoreaction of 2-(3-thiophenyl)-naphto[1,2-a]quinolizinium also gave azoniacoronene in 82% yield. Applying this new reaction, we tried to obtain 2a,8a-diazoniacoronene having two quaternary nitrogen atoms. Stepwised condensation of 2,8-dimethylquinolizinium with 3-thiophenaldehyde and pyridine-4-carboaldehyde afforded an unsymmetric diolefin. Photoreaction of the diolefin gave 2a,8a-diazoniacoronene in 5% yield with a pyridone type by-product. Diazonia derivative of doublecoronene was also obtained by this reaction.The azoniacoronene shows a strong luminescence in dilute solution. However, increase of solvent concentration or polarity, the fluorescence spectrum shifts to longer wavelength with decrease of the quantum yield due to self-aggregation confirmed by UV/vis, fluorescent, and NMR titration studies. We also found the fluorescent property of azoniacoronene-polyanion complexes, such as polyion-complex with anionic polymer or intercalated layered inorganic material, are depending on the polyanionic matrices, and the cation exchange ratio of the polyion complexes also affects the optical properties. Less