Ratiometric Fluorescent Detection of Chromium(III) Based on One-Dimensional Imine-Linked Covalent Organic Framework

Chromium (Cr³⁺) as a highly toxic pollutant has aroused much attention due to its wide industrial applications. Covalent organic frameworks (COFs) have been considered as one of the most promising metal ion sensors due to their open pore channels and abundant adsorption sites. Herein, a novel luminescent one-dimensional COF (Py-An COF) was constructed by the condensation of 5'-(anthracen-9-yl)-[1,1':3',1″-terphenyl]-4,4″-dicarbaldehyde (An-2CHO) and 1,3,6,8-tetrakis(p-aminophenyl) pyrene (PyTTA). The resulting COF showed high crystallinity, comparative high surface area, and good thermal stability, which can be utilized for Cr³⁺ fluorescent sensors with high sensitivity and selectivity. Furthermore, the coordination between Schiff-base N atoms and Cr³⁺ inhibits the photoinduced electron transfer (PET) process, resulting in the enhanced fluorescence intensity of chromophores (436 nm) and decreased the fluorescence intensity of Py-An COF (512 nm) simultaneously, which eventually realizes a highly efficient ratiometric fluorescent sensor for trace Cr³⁺. Compared with other porous fluorescent materials, Py-An COF possesses a lower detection limit, higher sensitivity, and better selectivity. This work provides strategic guidance for the design of COFs as ratiometric fluorescence sensors.