Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe³⁺ Ions

Herein, we report the synthesis of two new manganese-based luminescent metal-organic frameworks (LMOFs) [Mn_0.5(tipe)(1,4-ndc)] (1) and [Mn(tipe)(1,4-ndc) (H₂O)·(DMF)₂·(H₂O)₃] (2) [tipe = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethene (tipe) and 1,4-ndc = 1,4-naphthalenedicarboxylic acid] constructed from an aggregation-induced emission (AIE) chromophore ligand. Compound 1 can undergo a facile single-crystal-to-single-crystal transformation to form compound 2, which results in an increase in dimensionality from a two-dimensional (2D) network to a three-dimensional (3D) network. Both compounds demonstrate excellent performance for the solution-phase detection of Fe³⁺ ions through a significant and rapid quench in luminescence emission. Fluorescence titration experiments reveal that compound 2 is more selective toward Fe³⁺ compared to compound 1 because of its 3D stacking mode. The K _sv value for compound 2 (32 378 M^-1) is twice as large as that for compound 1 (15 854 M^-1) for the detection of Fe³⁺ ions. We attribute this significant increase in performance to the increase in dimensionality. In addition, compound 2 demonstrates high selectivity and sensitivity for the detection of Cr³⁺ cations and Cr₂O₇ ^2- anions.