Tetraphenylethene-based macrocycles: Visualized monitoring the hydrolysis of silicon-oxygen bond and their tunable luminescent properties

Abstract

The preparation of silicone material is generally carried out by hydrolytic condensation, and various methods have been tried so far to study the kinetics of silicon-oxygen bond hydrolysis. However, the process and kinetics of silicon-oxygen bond hydrolysis cannot be efficiently monitored in real-time due to the limitations of traditional testing methods. In the present study, we have successfully designed and synthesized a series of circular tetraphenylethylene (TPE) derivatives connected with different lengths of the siloxanes chain. As the chain length gets longer, the restriction on phenyl rotation in TPE derivatives becomes weaker, which induced fluorescence quenching gradually at the molecular level. Hence, it provides the most direct and convincing evidence for the effect of chain lengths in the popular restricted intramolecular rotation (RIR) mechanism with aggregation-induced emission (AIE) phenomenon. The strong fluorescent molecule was used to monitor the kinetics of silicon-oxygen bond hydrolysis in real-time successfully by the AIE method with the RIR mechanism. The high sensitivity and efficiency of fluorescence provide an unparalleled “visualization” window for real-time monitoring of the kinetic control of Si-O bond hydrolysis. Furthermore, the half-life and reaction kinetic data of Si-O bond-breaking reaction by different pH are obtained to provide a reference for scientists and engineers not only in fundamental research but also in industrial production. Finally, the aggregation-induced color-tunable emission was obtained with the different aggregation forms of molecules, exhibiting a promising potential for intelligent luminescent materials.