Series of Fluorescent Coordination Polymers Exhibiting Structural Evolution and Optimized Selective Ion Detection

Abstract

A series of Zn(II)-H 2 L (H 2 L = 3,3′-(9,9-diethyl-9H-fluorene-2,7-diyl)dibenzoic acid) fluorescent coordination polymers were synthesized using a mixed-ligand approach through solvothermal methods, demonstrating a structural transition from three-dimensional (3D) to two-dimensional (2D) frameworks. The structural evolution is driven by the gradational size variation of the pyridine-based ligands, L1 (9,10-di(4-pyridyl)anthracene), L2 (1,4-bis(pyridyl)benzene), and L3 (4,4′-bipyridine), resulting in distinct spatial packing and coordination modes. The polymers, designated as {[Zn 2 (L) 2 (L1)]} n ( 1 ), {[Zn 2 (L) 2 (L2)]} n ( 2 ), and {[Zn 2 (L) 2 (L3)]} n ( 3 ), feature a structural evolution from 3D interpenetrated to 2D alternating structures, significantly influencing their fluorescent properties for ion detection. Notably, compound 3 exhibits marked selectivity and sensitivity toward trivalent metal ions (Cr 3+, Al 3+, and Fe 3+ ) with detection limits of 0.19 μM for Cr 3+, 0.30 μM for Al 3+, and 0.37 μM for Fe 3+ . This research provides valuable insights into the designability of metal–organic frameworks and advances the development of MOF-based fluorescent probes for selective ion detection, highlighting the impact of systematic structural adjustments on ion selectivity and sensing performance.