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. 用双环辛烯骨架退火的脱氢轮烯。用双环-[2.2.2]辛烯退火的脱氢-[12]-、-[16]-、-[18]-、-[24]-和-[30]-轮烯（缩写为BCO）被合成并研究了它们的氧化还原行为，特别是[16]轮烯被发现与形成稳定的络合物。 2．BCO退火的苯环芳烃。合成了BCO完全退火的苯、萘、联苯、蒽，并转化为第一种稳定的自由基阳离子盐。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氧化成除阳离子之外的阳离子。 3. BCO三苯并环庚三烯和硅杂环庚三烯离子络合合成了一系列Si上带有不同取代基的BCO三苯并环庚三烯，并通过NMR方法阐明了它们的动力学行为。低温下在二氯甲烷溶液中转化为第一个硅托吡鎓离子，并求出硅托吡鎓离子的性质。通过D11D1H、D113D1C和D129D1Si核磁共振波谱证明了这一点。 4．BCO退火的含硫环状Pi系统。合成了1,2-和1,4-二硫英以及一个与两个BCO单元退火的噻吩，并将其转化为稳定的化合物。自由基阳离子的盐。进一步氧化成双阳离子，发现其是6-pi电子芳香系统，合成了在3,4位与BCO退火的噻吩并转化为聚噻吩衍生物。