New Ln-MOFs based on mixed organic ligands: synthesis, structure and efficient luminescence sensing of the Hg²⁺ ions...

In view of Hg²⁺ ion sensing by luminescence, a series of new, phenanthroline-decorated 3D lanthanide metal organic frameworks (Ln-MOFs) valorising an original combination of four different lanthanides and two organic ligands, i.e. thiobis(4-methylene-benzoic acid) (H₂tmba) and 1,10-phenanthroline (phen), have been successfully synthesized, namely {[Ln₄(tmba)₆(phen)₄]·m(H₂O)(phen)} [Ln = Ce, m = 3 (1); Pr, m = 1 (2); Eu, m = 3 (3); and Tb, m = 3 (4)]. Compounds 1-4 were characterised by single-crystal X-ray diffraction, elemental and thermogravimetric analyses, and powder X-ray diffraction. The luminescence properties of complexes 3 and 4 were thoroughly investigated. It is herein proved that compound 3 sensitively and selectively acts as an excellent luminescent probe for the detection of Hg²⁺ ions in waters, with a detection limit of 1.00 μM. As additional assets, 3 displays superb stability over a wide pH range (3-12) of the aqueous media, as well as convenient recycling after completion of the detection experiments. The rationale for the observed luminescence quenching effect of mercury might be a strong interaction arising between Hg²⁺ ions and the carboxylate oxygen atoms of the tmba^2- ligand. The results open new perspectives for applications in environmental remediation.