权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Synthesis and Physical Properties of Novel Cationic Disk-shaped Molecules

新型阳离子盘状分子的合成及物理性质

基本信息

批准号：
17550041
负责人：
SATO Kiyoshi
金额：
$ 1.34万
依托单位：
Tokyo Metropolitan University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

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

盘状多环芳烃“晕苯”是一种极具吸引力的有机分子，其结构特征在有机光电子材料和器件如柱状液晶、有机晶体管、电致发光显示器、有机太阳能电池等方面具有广阔的应用前景。用杂环取代晕苯的苯环将有望改变它们的电子和结构性质。一些杂冠（或杂环），包括噻吩，呋喃，或哒嗪环已被报道，直到现在。本研究通过光诱导偶氮[6]螺烯分子内Diels-Alder型反应合成了偶氮并[6]螺烯。辐射到，9-（2-萘基乙烯基）-噻吩并喹嗪盐的乙腈溶液中，以80%的产率得到偶氮二氢吡喃。 ...更多信息通过分子内光-Diels-桤木型反应，然后进行氧化-光环化反应。2-（3-噻吩基）-萘并[1，2-a]喹嗪鎓的光反应也得到了82%产率的偶氮蒽酮。应用这一新的反应，我们试图得到具有两个季氮原子的2a，8a-重氮并可罗烯。2，8-二甲基喹嗪鎓与3-噻吩甲醛和吡啶-4-甲醛的硬脂酰化缩合得到一种不对称二烯烃。二烯烃的光反应以5%的产率得到2a，8a-重氮蒽并伴有吡啶酮类副产物。通过该反应还得到了重氮的双冠烯衍生物，在稀溶液中表现出很强的发光。然而，溶剂浓度或极性的增加，荧光光谱移到较长的波长与量子产率的降低，由于自聚集的UV/维斯，荧光，和NMR滴定研究证实。我们还发现，偶氮可酮-聚阴离子复合物（如聚离子与阴离子聚合物的复合物或插层无机材料）的荧光性质取决于聚阴离子基质，并且聚离子复合物的阳离子交换比也影响其光学性质。少