Dual-Ligand Strategy Employing Rigid 2,5-Thiophenedicarboxylate and 1,10-Phenanthroline as Coligands for Solvothermal Synthesis of Eight Lanthanide(III) Coordination Polymers: Structural Diversity, DFT Study, and Exploration of the Luminescent Tb(III) Coordination Polymer as an Efficient Chemical Sensor for Nitroaromatic Compounds

[Image: see text] Lanthanide coordination polymers (Ln-CPs) are potential chemosensors when fabricated to depict a detectable change in optical properties on interaction with target analytes. This work investigates the interaction of nitroaromatic compounds with Ln-CPs leading to induced changes in fluorescence emission intensity, a crucial strategy to develop a selective and sensitive system for the sensing of nitroaromatics. Approaching toward this objective, solvothermal reactions of 2,5-thiophenedicarboxylic (2,5-TDC) acid, 1,10-phenanthroline (1,10-Phen), and Ln(NO(3))(3)·xH(2)O are carried out to assemble eight Ln(III) coordination polymers [Ln(2)(2,5-TDC)(3)(1,10-Phen)(2)(H(2)O)(2)] [Ln = Pr (1), Nd (2)], {[Tb(2,5-TDC)(1.5)(1,10-Phen)(H(2)O)]·DMF} (3), and [Ln(2,5-TDC)(1.5)(1,10-Phen)]·xH(2)O (Ln = Tb (4), Dy (5), Ho (6), Er (7), and Yb (8)); x = 0 for CP 4, 5, 6, and 8 and x = 1 for CP 7 with two different space groups and dimensions. The as-synthesized polymers 1–8 are characterized by powder X-ray crystallography, infrared spectroscopy, and thermogravimetric analysis. The structure-corroborated density functional theory (DFT) studies are done on the selected CPs to investigate the interactions between different structural motifs of the assembled CPs. The luminescence properties of CP 4 are explored in detail and are found to be highly sensitive for the detection of p-nitrotoluene as indicated by the most intensive fluorescence quenching with the lowest limit of detection (0.88 ppm) and high quenching constant (4.3 × 10(4) M(–1)). Other nitro compounds (viz., o-nitrobenzaldehyde, m-nitroaniline, picric acid, m-dinitrobenzene, p-nitrophenol, and p-nitroaniline) are also screened for potential sensing by CP 4.