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Organometallic chemistry of carbon allotropes: extension to two-dimensional systems and applications to highly functionalized systems.

碳同素异形体的有机金属化学：扩展到二维系统和在高功能化系统中的应用。

基本信息

批准号：
15350032
负责人：
AKITA Munetaka
金额：
$ 9.6万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2006
项目状态：
已结题

项目摘要

We have been studying organometallic chemistry of polynuclear species containing carbon allotropes. In this study our research activity was focused on development of higher dimensional and highly functional molecular wires, which are indispensable components of "molecular circuit"1.Synthetic study of higher dimensional molecular wiresAs the two- and three-dimensional skeletons, ethylene and cyclophane were chosen and the redox-active iron fragments were attached to the organic cores. We established that, if the bulky organometallic fragments were separated enough, the desired polynuclea species were prepared successfully. The obtained compounds were characterized spectroscopically and crystallographically, and their performances as molecular wires was characterized by means of the electrochemical methods.The above-mentioned synthetic study also provided dinuclear complexes with endiyne bridges. Their performance as molecular wires can be tuned by the introduction of substituents on the olefinic moiety and, in the case of the aryl derivatives, the performance was superior to that of the polyyneduyl complex, which was regarded as the most efficient organometallic molecular wire.2.Introduction of switching functionIntroduction of switching function was examined. The photochromic dithienylethene (DTE) bridge was employed and the desired compound was obtained by the synthetic method via a vinylidene intermediated and characterized spectroscopically and crystallographically. The DTE complex showed photochromic behavior analogous to the organic counterparts and the ON/OFF ratio of the Kc values was as large as 39 and much larger than the previously reported molecular switches. Molecules containing pH-sensitive functional groups were also studied.The above-mentioned obtained results will contribute to the development of the molecular circuit.

我们一直在研究含碳同素异形体的多核物种的有机金属化学。在这项研究中，我们的研究活动集中在开发高维和高功能的分子线，这是“分子电路”1不可或缺的元件。高维分子线的合成研究选择了乙烯和环番作为二维和三维骨架，并将氧化还原活性的铁片段连接到有机核心上。我们证实，如果将庞大的有机金属碎片充分分离，就能成功地制备出所需的多核物种。对所合成的化合物进行了光谱和结晶学表征，并用电化学方法对其作为分子导线的性能进行了表征。上述合成研究还为双核配合物提供了endiyne桥。它们作为分子导线的性能可以通过在烯烃部分引入取代基来调节，对于芳基衍生物，其性能优于被认为是最有效的有机金属分子导线的聚乙炔配合物。2.开关函数的引入。采用光致变色二硫代乙烯(DTE)桥的方法，以亚乙叉为中间体合成了目标化合物，并进行了光谱和结晶学表征。DTE络合物表现出与有机络合物相似的光致变色行为，Kc值的开/关比高达39，远远大于已报道的分子开关。对含有pH敏感官能团的分子也进行了研究，上述结果将有助于分子电路的发展。