Intense multi-colored luminescence in a series of rare-earth metal–organic frameworks with aliphatic linkers

Abstract

Two series of highly luminescent yttrium(III), europium(III) and terbium(III) metal–organic frameworks containing diimine aromatic ligands and the dicarboxylate linker trans-1,4-cyclohexanedicarboxylate (chdc²⁻) which can be described by the general formulas [M₂(bpy)₂(chdc)₃], where M = Y³⁺ (1), Eu³⁺ (2), and Tb³⁺ (3) and bpy = 2,2′-bipyridyl, and [M₂(phen)₂(chdc)₃], where M = Y³⁺ (4), Eu³⁺ (5), and Tb³⁺ (6) and phen = 1,10-phenanthroline, were synthesized and characterized. All compounds are based on the same dinuclear {M₂(L)₂(OOCR)₆} building blocks and possess a similar topology of the 3D framework with narrow pores. The chelate aromatic ligands act as efficient light-harvesting antennas for subsequent energy transfer to the emitting metal center (M = Eu³⁺, Tb³⁺) or intraligand photoemission (M = Y³⁺). As a result, the reported compounds display intense emission in the red (Eu³⁺), green (Tb³⁺) or blue (Y³⁺) regions representing three basic colors (RGB) of visible light. The measured quantum yields (QYs) of the solid-state luminescence for individual compounds were found to be 63% (1), 46% (2), 59% (3), 2.3% (4), 55% (5) and 49% (6). The drastic reduction of the luminescence efficiency for 4 is explained by the strong disorder of phen ligands. The high thermal stability (up to 300 °C) and exceptional moisture resistance of the bpy-based frameworks 1–3 were confirmed by TG and PXRD measurements. Various bimetal or trimetal compositions were also prepared for the bpy-series. The luminescence properties of these mixed-metal compounds depend on both the chemical composition and excitation wavelength (λ_ex). Remarkably, pure white emission with color temperature = 6126 K was achieved for [Y_1.68Eu_0.08Tb_0.24(bpy)₂(chdc)₃] at λ_ex = 360 nm with QY = 20%. The reported results suggest that the obtained coordination framework series is a convenient platform for the design of highly efficient light emitting materials with tunable properties.