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Design and Synthesis of Model Compounds for Functional Materials Based on σ-π Conjugation

基于σ-π共轭的功能材料模型化合物的设计与合成

基本信息

批准号：
09304060
负责人：
KOMATSU Koichi
金额：
$ 2.69万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

1. Dehydroannulenes Annelated with Bicyclooctene Frameworks.Dehydro-[12]-, -[16]-, -[18]-, -[24]-, and -[30]-annulenes annelated with bicyclo-[2.2.2] octene (abbreviated as BCO) were synthesized and their redox behaviors investigated. Particularly the [16] annulene was found to form a stable complex with silver(I)ion, which structure was clarified by X-ray crystallography.2. Benzenoid Aromatic Hydrocarbons Annelated with BCO.Benzene, naphthalene, biphenylene, and anthracene fully annelated with BCO were synthesized and transformed into the first stable salts of the radical cations. The structures were determined by X-ray crystallography, and were interpreted by theoretical calculations. The radical cations were further oxidized to dications except the benzene derivative.3. Silacycloheptatriene and Silatropylium Ion Annelated with BCO.A series of silacycloheptatrienes tris-annelated with BCO and having various substituents on Si were synthesized and their dynamic behavior clarified by the NMR method. The derivative having a mesityl group on Si was successfully transformed into the first silatropylium ion in dichloromethane solution at low temperature. The silylium-ion character was demonstrated by the ィイD11ィエD1H, ィイD113ィエD1C, and ィイD129ィエD1Si NMR spectroscopy.4. Sulfur-Containing Cyclic Pi-Systems Annelated with BCO.The 1,2-and 1,4-dithiins and a thiophene annelated with two BCO units were synthesized and transformed into stable salts of the radical cations. The dithiins were further oxidized to dications, which were found to be the 6-pi electronic aromatic systems. A thiphene annelated with BCO at 3,4-positions was synthesized and transformed into the polythiophene derivative.

1. 双环辛烯骨架退火的脱氢轮烯。合成了双环[2.2.2]辛烯（简称BCO）退火的脱氢-[12]-、-[16]-、-[18]-、-[24]-和-[30]-轮烯，并研究了它们的氧化还原行为。特别是[16]轮烯与银(I)离子形成稳定的络合物，并通过X射线晶体学阐明了其结构。 2． BCO 稠合的苯环芳烃。合成了与 BCO 完全稠合的苯、萘、联苯撑和蒽，并将其转化为自由基阳离子的第一种稳定盐。通过X射线晶体学确定结构，并通过理论计算解释。自由基阳离子进一步被氧化成除苯衍生物以外的双阳离子。 3．硅杂环庚三烯和硅杂环庚三烯与BCO离子退火。合成了一系列硅杂环庚三烯与BCO三退火并在Si上具有各种取代基，并通过NMR方法阐明了它们的动态行为。 Si上带有基团的衍生物在二氯甲烷溶液中低温下成功转化为第一个硅杂吡鎓离子。ィイD11ィエD1H、ィイD113ィエD1C、ィイD129ィエD1Si核磁共振波谱证实了硅离子的特征。4．与 BCO 退火的含硫环状 Pi 系统。合成了与两个 BCO 单元退火的 1,2-和 1,4-二噻英以及噻吩，并将其转化为自由基阳离子的稳定盐。二硫苷进一步氧化成双阳离子，这就是 6-pi 电子芳香系统。合成了在 3,4 位与 BCO 退火的噻吩并将其转化为聚噻吩衍生物。