Pyrazine Functionalization in Eu-MOF for Exclusive Ratiometric Luminescence Sensing of PO43–

Single-emission luminescence sensors are less than satisfactory for complex systems due to their susceptibility to environmental disturbances. Lanthanum-based metal–organic frameworks (Ln-MOFs) with highly stable ratiometric dual-emission are regarded as promising luminescence probes owing to their fascinating ligand-to-metal energy transfer behaviors (also known as the antenna effect). Herein, we report the synthesis of a pair of isostructural europium-based MOFs (termed JNU-219 and JNU-220) by utilizing two X-shaped tetracarboxylate linkers, 4,4′,4″,4‴-benzene-2,3,5,6-tetrayl-tetrabenzoate (BTEB) and 4,4′,4″,4‴-pyrazine-2,3,5,6-tetrayl-tetrabenzoate (BTTB). Both JNU-219 and JNU-220 present the characteristic red luminescence of Eu3+, yet the pyrazine functionalization of the BTTB linker renders JNU-220 with significantly increased luminescence emission, almost 30 times that of JNU-219. As a result, the detection limit of JNU-220 for the ratiometric luminescence sensing of PO43– was determined to be as low as 0.22 μM, which is far superior to those of other reported MOF materials. Additionally, we demonstrate the excellent stability and reusability of JNU-220, further verifying its potential as a robust ratiometric luminescence probe.