H. Kanazawa, M. Higuchi, K. Yamamoto
J. Am. Chem. Soc. 2005, 127, 16404-16405.
An Electric Cyclophane: Cavity Control Based on the Rotation of a Paraphenylene by Redox Switching
Although a free rotation around a single bond gives no mechanical output, it has let us imagine a molecular motor. A para-substituted aromatic ring can be regarded as a rotator with the para-rotation axis. When it is incorporated in a wider π-conjugated system, a quinoidal structure is generated accompanied by oxidation on the substituted groups at the 1,4-position, and the axis is fixed. A paraphenylenediamine was selected as the nanomechanical molecular module capable of locking and releasing the free rotation using an electrode in solution. We inserted the module into a simple molecular system, cyclophane. It was clarified that the cyclophane was able to open and close its cavity in a reversible redox process repeatedly.