3D lanthanide-coordination frameworks constructed by a ternary mixed-ligand: crystal structure, luminescence and luminescence sensing†
Using a mixed ligand synthesis strategy involving semi-rigid 4-(4-carboxyphenoxy)-isophthalic acid (cphtH3), oxalate (ox) as a mixed linker and 1,10-phenanthroline (phen) as an ancillary terminal ligand, a series of highly stable metal coordination frameworks, Ln-MOFs, [Ln(cphtH)phen(ox)0.5]n·mH2O (Ln = Sm 1, Eu 2, Gd 3, Tb 4 and Dy 5), were synthesized. They are isostructural 3D coordination networks of interlinked left- and right-handed helices based on [LnO7N2] connections. The Brunauer–Emmett–Teller (BET) surface area was 3.3020 m2 g−1 (Langmuir surface area: 3.6940 m2 g−1). They are chemically stable in common solvents and are stable in aqueous solutions from pH = 4 to 9. Complexes 1 and 5 are dual-emissive materials exhibiting a broad emission band from the π*–π transition of the organic linker and narrow emission peaks, the 4G5/2 → 6HJ (J = 5/2, 7/2, and 9/2) transitions of the Sm3+ ion for 1 and 4F9/2 → 6HJ (J = 15/2 and 13/2) transitions of the Dy3+ ion for 5. Complexes 2 and 4 exhibit red and green emission, assigned to the 5D0 → 7FJ (J = 1–2) transitions of the Eu3+ ion and 5D4 → 7FJ (J = 6–3) transitions of the Tb3+ ion, respectively. The maximum excitation wavelengths are 356, 358, 360 and 350 nm for 1, 2, 3 and 4, respectively, which are in the near-visible radiation region (350 nm < λex < 420 nm). The Sm-MOF (1) displays a single component white light based on its dual-emission. The primary focus of this study is to examine the fluorescence properties of Eu-MOF (2) as it showed excellent luminescence in solvent as well as aqueous solutions over a wide pH range (pH = 4–9). Based on the luminescence quenching of the Eu-MOF, the detection of quercetin in water and Fe3+ ions in several solvent systems was realized at a long maximum excitation wavelength of 358 nm.