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

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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.