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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.双环辛烯环化脱氢轮烯合成了双环[2.2.2]辛烯环化脱氢-[12]-、-[16]-、-[18]-、-[24]-和-[30]-轮烯（简称BCO），并研究了它们的氧化还原行为。特别是[16]轮烯与银（I）离子形成了稳定的配合物，其结构通过X射线晶体学得到了证实.苯、萘、联苯、蒽与BCO完全成环，并转化为自由基阳离子的第一稳定盐。通过X射线晶体学确定了结构，并通过理论计算进行了解释。除苯衍生物外，自由基阳离子被进一步氧化成双阳离子.硅杂环庚三烯和硅杂环庚三烯离子与BCO成环合成了一系列硅杂环庚三烯与BCO成环的硅杂环庚三烯衍生物，并通过核磁共振研究了它们的动力学行为。在低温二氯甲烷溶液中，硅上带有异亚丙基甲基的衍生物成功地转化为第一个硅托吡唑。硅离子的特征通过核磁共振谱图中的D11硅D1 H、D113硅D1C和D129硅D1 Si得到证实。含硫环π-体系与BCO的配位合成了1，2-和1，4-二噻英以及一个与两个BCO单元配位的噻吩，并将其转化为稳定的自由基阳离子盐。二噻英进一步被氧化成双阳离子，这被认为是6-π电子芳香系统。合成了在3，4位与BCO稠合的噻吩并将其转化为聚噻吩衍生物。