Theoretical and experimental studies on mechanochromic triphenylamine based fluorescent ON-OFF-ON sensor for sequential detection of Fe3+and deferasirox

A novel triphenylamine (TPA) based sensor TTU was rationally designed and synthesized that exhibited reversible mechanochromic and aggregation induced emission enhancement (AIEE) properties. The AIEE active sensor was employed for fluorometric detection of Fe3+ in aqueous medium, with distinguished selectivity. The sensor showed a highly selective quenching response towards Fe3+ that is ascribed to complex formation with paramagnetic Fe3+. Subsequently, TTU-Fe3+ complex acted as a fluorescence sensor for the detection of deferasirox (DFX). The subsequent addition of DFX to TTU-Fe3+ complex led to the recovery of fluorescence emission intensity of sensor TTU that was attributed to the displacement of Fe3+ by DFX and release of sensor TTU. The proposed sensing mechanisms for Fe3+ and DFX was confirmed through 1H NMR titration experiment and DFT calculations. Frontier molecular orbitals (FMO), density of states (DOS), natural bond orbital (NBO), noncovalent interaction (NCI) and electron density difference (EDD) analysis were performed using DFT calculations to support the experimental results. Moreover, sensor TTU displayed colorimetric detection of Fe3+. Further, the sensor was employed for the detection of Fe3+ and DFX in real water samples. Finally, logic gate was fabricated by using sequential detection strategy.

Automated summary

A novel sensor TTU, based on triphenylamine (TPA), was designed and synthesized with reversible mechanochromic and aggregation induced emission enhancement (AIEE) properties. The sensor showed distinguished selectivity and was employed for fluorometric detection of Fe3+ in aqueous medium. Furthermore, the sensor acted as a fluorescence sensor for the detection of deferasirox (DFX) by displacing Fe3+ and releasing sensor TTU. The proposed sensing mechanisms for Fe3+ and DFX were confirmed through experiments and calculations.