A Novel Ratiometric Fluorescent Mercury Probe Based on Deprotonation-ICT Mechanism.

A new NBD-rhodamine dye (1) was developed as a colorimetric and ratiometric fluorescent chemosensor for Hg(2+) with good selectivity in aqueous ethanol solutions under neutral to basic conditions. Sensor 1 showed absorption at 468 nm and a weak emission at 529 nm (ϕ F  = 0.063) in ethanol/aqueous tris buffer (9:1, v/v) of pH 9.17 solution. Bathochromic shifts in both absorption (492 nm) and fluorescence spectra (569 nm, ϕ F  = 0.129), respectively upon addition of 2 equiv. of Hg(2+) were observed. The ring-opening reaction of the spirolactam form to the corresponding xanthene form was not found. The interaction of Hg(2+) with chemosensor 1 resulted in the deprotonation of the secondary amine conjugated to the NBD component so that the electron-donating ability of the N atom was enhanced. Deprotonation-ICT mechanism of secondary amines was suggested for the ratiometric fluorescent chemosensing for Hg(2+).