Ultrasensitive Colorimetric and Ratiometric Detection of Cu²⁺: Acid–Base Properties, Complexation, and Binding Studies

Abstract

Herein, we report the synthesis and characterization of a chemosensor, 5-(diethylamino)-2-(2,3-dihydro-1<i>H</i>-perimidin-2-yl)phenol (H<b>L</b>), synthesized from a condensation between 4-(diethylamino)salicylaldehyde and 1,8-diaminonaphthalene. Upon investigation of the sensing properties of H<b>L</b>, it was found that this sensor may be employed for simple yet efficient detection of Cu²⁺ in aqueous methanol solutions. The selective and ratiometric response to Cu²⁺ yielded an outstandingly low limit of detection of 3.7 nM by spectrophotometry and is also useful as a naked-eye sensor from 2.5 μM. The system was studied by spectrophotometric pH titrations to determine Cu²⁺ binding constants and complex speciation. Binding of Cu²⁺ to H<b>L</b> occurs in 1:1 stoichiometry, in good agreement with high-resolution electrospray ionization mass spectrometry (ESI-HRMS) results, Cu²⁺ titrations, and Job's plot experiments, while the coordination geometry was tentatively assigned as square pyramidal by spectroscopic studies.