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

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。本论文的研究工作主要集中在开发“分子电路“中不可缺少的高维高功能分子导线上。1.高维分子导线的合成研究选用乙烯和环蕃作为二维和三维骨架，并将具有氧化还原活性的铁片段连接到有机核上。我们确定，如果大体积的有机金属片段被分离得足够，所需的多核物种被成功地制备。对所得化合物进行了光谱和晶体学表征，并通过电化学方法对它们作为分子导线的性能进行了表征，上述合成研究还提供了含烯二炔桥的双核配合物。它们作为分子导线的性能可以通过在烯烃部分上引入取代基来调节，并且在芳基衍生物的情况下，性能上级于被认为是最有效的有机金属分子导线的聚炔基配合物的性能。2.开关功能的引入开关功能的引入进行了检查。采用二噻吩基乙烯（DTE）光致变色桥，通过亚乙烯基中间体合成了目标化合物，并对其进行了光谱和晶体学表征。DTE配合物表现出类似于有机对应物的光致变色行为，并且Kc值的ON/OFF比高达39，远大于先前报道的分子开关。对含pH敏感功能基团的分子也进行了研究，所得结果将有助于分子电路的发展。

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.