Step-by-step reaction-powered mechanical motion triggered by a chemical fuel pulse

Abstract

Natural molecular machines perform important tasks in organisms under a reasonable energy supply strategy: a series of step-by-step biochemical reactions after the intake of a fuel such as glucose. As analogues of biomolecular machines, most artificial molecular machines and shuttles are still powered by two opposite stimuli, such as acid and base or oxidation and reduction. This inconvenient stimulus method for artificial molecular machines and shuttles creates great obstacles for realizing more functions of artificial molecular machines and shuttles owing to low energy utilization efficiency and troublesome operation. In this work, we report a new step-by-step reaction system combining two known reactions: (1) the formation of [bis(trifluoroacetoxy)iodo]benzene from the reaction of iodosylbenzene and trifluoroacetic acid; and (2) the catalytic oxidation of alcohols by [bis(trifluoroacetoxy)iodo]benzene in the presence of TEMPO. Owing to the acid absorption features of the first reaction and the acid releasing characteristics of the second reaction, the new step-by-step reaction obtains a pH oscillation feature. Taking advantage of the pH oscillation feature, the new reaction cycle triggered by iodosylbenzene was coupled with an acid–base switchable helicarene-based molecular shuttle. Benefitting from the reaction rate difference of the two known reactions (the reaction rate of the first reaction is faster than that of the second reaction), the movement of the helicarene on the axle could be controlled automatically by the reaction system through adding iodosylbenzene to a solution of alcohol, TEMPO and protonated rotaxane, and the manual addition of another opposite stimulus could be avoided.