Photothermal-responsive [2]rotaxanes

Abstract

Three photothermal-responsive α-cyclodextrin-based [2]rotaxanes were prepared via the copper(I)-catalyzed azide–alkyne cycloaddition, in which the α-cyclodextrin ring was threaded onto the azobenzene dumbbell component. The difference between the three [2]rotaxanes are the length of the ethylene glycol repeating chains connected between the azobenzene and triazole units in the dumbbell components. The α-cyclodextrin rings in the [2]rotaxanes can be reversibly switched between the azobenzene unit and triazole/ethylene glycol unit driven by the trans–cis isomerization of the azobenzene unit. The trans-to-cis isomerization of the azobenzene unit under UV light irradiation (365 nm) leads the α-cyclodextrin ring moving to the triazole/ethylene glycol unit, while the cis-to-trans isomerization of the azobenzene unit under either visible light irradiation or heating enables the α-cyclodextrin ring shuttling back to the azobenzene station. The different ethylene glycol repeating chains in the [2]rotaxanes can affect (1) the isomerization rates of the azobenzene units, i.e. the longer the chain, the faster the isomerization rate, and (2) fluorescent quantum yields of the [2]rotaxanes, i.e. the longer the chain, the lower the fluorescent quantum yield. In addition, the quantum yields of the [2]rotaxanes were enhanced by UV light irradiation and decreased back upon visible light irradiation or heating at 65 °C. The current research provides a fundamental understanding of the working mechanism for photothermal-responsive [2]rotaxanes.