Self-assembly, stability quantification, controlled molecular switching, and sensing properties of an anthracene-containing dynamic [2]rotaxane

Abstract

The preparation of a novel anthracene-containing dynamic [2]rotaxane by a templating self-assembly process between a diamine and a dialdehyde to form a [24]crown-8 macrocyclic diimine, in the presence of a dumbbell containing a secondary dialkylammonium ion center as the template, which has been exploited for its sensing properties. By appealing to the ability of the anthracene ring system - one of the two stoppers associated with the dumbbell - to act as a fluorescent probe, the fluorescence and fluorescence-quenching nature of the dynamic rotaxane in an equilibrium mixture has been investigated and quantified in the presence of external stimuli such as water, acids, salts, and an amine. The stability, as expressed by the hydrolysis of the dynamic rotaxane has been monitored by following: (i) the anthracene fluorescence and (ii) the movements of the signals in the 1H NMR spectra. The rate of hydrolysis (t 1/2 = 6.9 min) of the dynamic rotaxane in the presence of a small amount (1 equiv.) of acid was found to be very much faster than when the hydrolysis was carried out with a large amount (>100 equiv.) of water, when t1/2 > 140 min. Furthermore, it has been established that the anthracene fluorescence of the dynamic rotaxane rises with an increasing amount of acid. Two acid sensors have been identified with different operating modes - namely, logarithmic and linear. The combination of different inputs involving water, acids, salts and an amine leads to different fluorescence outputs from the dynamic rotaxane, hence, producing a prototype for expressing molecular logic. © 2010 The Royal Society of Chemistry.