A Selective and ''Off-On'' Fluorescent Chemosensor Based on Fluorescein for Al3+: Synthesis, Characterization, Spectroscopy Analyses, and DFT Calculation

J Fluoresc. 2023 Mar;33(2):639-651. doi: 10.1007/s10895-022-03087-x. Epub 2022 Dec 6.

Abstract

An efficient fluorescent cation chemosensor based on fluorescein L4 was well prepared and identified with spectroscopy analyses. UV-vis and fluorescence measurements examined the analyte complexation of the L4 with various cations, demonstrating a clear tendency to Al3+ ion. In the Job plot study, a stoichiometry ratio of a complex between L4 and Al3+ ion was determined to be 1: 2 (L4: Al3+). A stoichiometry ratio of complex between L4 and Al3+ ion was determined to be 1: 2 (L4: Al3+) using the Job plot. The association constant (Ka) of the L4-Al3+ complex was found 2.8 × 107 M-2. The obtained limit of detection (LOD) value (1.37 × 10-6 M for Al3+) exhibited the considerable sensitivity of the chemosensor L4 to Al3+ ion. DFT/TD-DFT calculations have also been employed to support the binding mode and photophysical properties of the complexation of chemosensor L4 to Al3+ ion and also to investigate the enhancement of L4 fluorescence by Al3+ ion.

Keywords: Aluminium ion; Chemosensor; DFT calculation; Fluorescein; Fluorescent ligand; Host–guest chemistry.