トリプチセン骨格の動力学
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概要
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Molecular dynamical aspects of triptycene molecules are discussed. After a short introduction to many interesting facets of triptycene chemistry, correlated internal rotation in bis (9-triptycyl) -X type molecules is described. Strict coupling of the rotation around the two C-X bonds was realized for the first time in these molecules in the shape of a bevel gear. In spite of the rapid geared rotation, the disrotatory motion gave birth to new stereoisomerism due to different phase relationship between the labeled cogs on the two wheels. The number of possible isomers is counted. Potential energy barriers associated with the gear meshing and gear clashing processes are discussed.<BR>Photoexcitation of triptycenes produces the molecules in the excitonic state from which unique chemistry of direct bonding between two of the three benzene rings with expulsion of the bridgehead atom as the monocentric diradical species, namely, carbenes and nitrenes, emerges. Mechanistic details of the reaction are given for 1-azatriptycene.
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