Evaluating the merit of a diethylamino coumarin-derived thiosemicarbazone as an intramolecular charge transfer probe: efficient Zn(ii) mediated emission swing from green to yellow

Abstract

We report the synthesis and photophysical properties of a coumarin based probe (1E)-1-(1-(7-(diethylamino)-2-oxo-2H-chromen-3-yl) ethylidene) thiosemicarbazide (DIDOT). DIDOT shows a polarity dependent change in the emission maxima in the solution phase. This is explained by the increased dipole moment in the excited state by an intramolecular charge transfer (ICT) process. DIDOT can successfully detect Zn(II) in aqueous methanol by a shift in the charge transfer emission maxima from approximately 506 to approximately 535 nm. This shift led to a change in the color of the emission from green to yellow under UV-light. The mechanism of Zn(II) detection has been delineated using electrospray ionization-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR) and fluorescence time resolved studies coupled with theoretical calculations. The increment in the charge transfer in the Zn(II) complex of DIDOT over the bare receptor as a consequence of conformational locking was determined to be the underlying cause of the cation detection phenomenon. The limit of detection and binding constant values of DIDOT towards Zn(II) were approximately 3 × 10⁻⁸ M and 2.35 × 10⁵ M⁻¹ respectively. Finally, the practical utility of DIDOT has been demonstrated by successful detection and quantification of Zn(II) in spiked water samples.