Unexpected Fluorescence Emission Behaviors of Tetraphenylethylene-Functionalized Polysiloxane and Highly Reversible...

Tetraphenylethylene (TPE), a typical luminogen with aggregation-induced emission (AIE) features, has been widely used to prepare AIE fluorescent materials. In this study, TPE-functionalized polydimethylsiloxane (n-TPE-AP-PDMS) was successfully synthesized by attaching TPE to polydimethylsiloxane via aza-Michael addition. The introduction of polydimethylsiloxane to TPE had no obvious effect on photophysical properties. Intriguingly, n-TPE-AP-PDMS exhibited two opposite fluorescence emission behaviors in different systems: aggregation-induced quenching (ACQ) behavior in a tetrahydrofuran/water mixture and typical AIE phenomenon in a tetrahydrofuran/hexane mixture. This unexpected transition from ACQ to AIE can be attributed to a twisted intramolecular charge-transfer effect and flexible aminopropyl polydimethylsiloxane. n-TPE-AP-PDMS was further used as a fluorescent probe to detect nitrobenzene and it showed high quenching efficiency. Moreover, the n-TPE-AP-PDMS film showed high reversibility so that the quenching efficiency remained constant after five cycles. This work can provide a deeper understanding of AIE behavior and guidance to develop a new AIE polymer for chemosensors with high performance.