Abstract
We construct a fluorescent supramolecular system (TPE-Q4⊂ DSP5) of excellent tolerance to a wide range of pH by the facile self-assembly of a new pillar[5]arene bearing disulfonated arms (DSP5) with an AIE-active tetraphenylethene-based tetratopic guest bearing four quaternary ammonium binding sites (TPE-Q4), which exhibits strong blue emission even in dilute aqueous solutions along with much higher quantum yield and longer fluorescence lifetime than TPE-Q4 itself. This appreciable property can be attributed to the supramolecular assembly-induced emission (SAIE) mechanism endowed by the host-guest inclusion complexation based on synthetic macrocycles. Remarkably, the enhanced fluorescence of the supramolecular assembly is quenched efficiently and exclusively by ferric ions in water with a high Stern–Volmer formula constant of 1.3 × 105 mol−1, demonstrating the excellent cation selectivity and visualized responsiveness in ion sensing and detection.
Highlights
Fluorescent supramolecular assemblies represent an extraordinarily attractive class of functional systems, due to their integrated functionalities, highly tunable fluorescence properties, and good responsiveness towards external stimuli [1]
In 2001, Tang and coworkers discovered some propeller-like molecules with π-conjugated structures that exhibited weak fluorescence in solution but bright emission in aggregated states in sharp contrast to traditional fluorescent molecules of aggregation caused quenching (ACQ) and creatively named this phenomenon aggregation-induced emission (AIE) [3]
In 2014, Tang and coworkers covalently linked a cyclodextrin with tetraphenylethene (TPE) and utilized self-inclusion complexation for restriction of intramolecular motion (RIM) to achieve enhanced emission in aqueous solutions, which represented the prototype supramolecular assembly-induced emission (SAIE) study and paved the way of recruiting supramolecular macrocycles to manipulate the fluorescent properties of AIEgens [6]
Summary
Fluorescent supramolecular assemblies represent an extraordinarily attractive class of functional systems, due to their integrated functionalities, highly tunable fluorescence properties, and good responsiveness towards external stimuli [1]. Inspired by the mechanism of AIE, researchers have successfully developed a supramolecular pathway, namely, supramolecular assembly-induced emission (SAIE), to achieve effective emission enhancement of AIEgens in the ordered assembly states no matter in dilute solutions or aggregated solid states [2, 6,7,8,9,10,11,12,13,14,15,16,17,18,19]. In 2014, Tang and coworkers covalently linked a cyclodextrin with tetraphenylethene (TPE) and utilized self-inclusion complexation for RIM to achieve enhanced emission in aqueous solutions, which represented the prototype SAIE study and paved the way of recruiting supramolecular macrocycles to manipulate the fluorescent properties of AIEgens [6]. Various types of supramolecular fluorescent assemblies based on AIEgens and functional synthetic macrocycles have been reported for applications in cell imaging, [11] fluorescent supramolecular polymers and gels [7,8,9,10, 13, 14], Research
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