Synthetic approaches for accessing rare-earth analogues of UiO-66

Rare-earth (RE) analogues of UiO-66 with non-functionalised 1,4-benzenedicarboxylate linkers are synthesised for the first time, and a series of synthetic approaches is provided to troubleshoot the synthesis. RE-UiO-66 analogues are fully characterised, and demonstrate a high degree of crystallinity, high surface area and thermal stability, consistent with the UiO-66 archetype

Rare-Earth Acetates as Alternative Precursors for Rare-Earth Cluster-Based Metal–Organic Frameworks

RE-UiO-66 analogues are synthesized using RE acetates as precursors for the first time. These MOFs are fully characterized and the influence of the precursor on the materials obtained is studied. Additionally, the influence of water on the yield of the syntheses and the quality of the materials is explored

Tuning the rare-earth UiO-66 metal–organic framework platform for white light emission

Metal–organic frameworks (MOFs) have received notable attention owing to their structural diversity, permanent porosity, and high surface areas. In addition to these properties, rare-earth (RE) MOFs have the added feature of tunable photoluminescence dictated by the identity of the metal ion and organic linker in the RE-MOF. Herein, we explore the tunable photoluminescent properties of RE-UiO-66 by synthesizing and characterizing mono-, bi- and tri-metal RE-UiO-66 analogues where RE = Tb(III), Gd(III), and Eu(III), to ultimately design a white light emitting MOF. The photophysical properties of this series of MOFs are explored and, as a proof of concept, the tri-metal Tb:Gd:Eu-UiO-66 is used as a surface coating on a UV light emitting diode (LED) to give a white light emitting device

Deciphering Trends in Structural Parameters of RE-UiO-66 Metal–Organic Frameworks through Single Crystal Analysis

Single crystals of a family of rare-earth metal–organic frameworks (RE-MOFs), RE-UiO-66 where RE = Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III), are successfully synthesized and their structures re-solved through single-crystal X-ray diffraction. Different structural parameters including unit cell dimensions and bond distances are explored to discover trends between those structural parameters, ionic radii of the RE ions in the MOF structures, and their thermal stability. Results suggest that subtle differences in metal-linker bond length can have a notable effect on thermal stability (+/- 60 °C)

Synthetic Approaches for Accessing Rare-Earth Analogues of UiO-66

Rare-earth (RE) analogues of UiO-66 with non-functionalised 1,4-benzenedicarboxylate linkers are synthesised for the first time, and a series of synthetic approaches is provided to troubleshoot the synthesis. RE-UiO-66 analogues are fully characterised, and demonstrate a high degree of crystallinity, high surface area and thermal stability, consistent with the UiO-66 archetype

Remodelling a Shp: Transmetallation in a Rare-Earth Cluster-Based Metal–Organic Framework

Post-synthetic modification (PSM) of metal–organic frameworks (MOFs) is an important strategy for accessing MOF analogues that cannot be easily synthesized de novo. In this work, the rare-earth (RE) cluster-based MOF, Y-CU-10, with shp topology was modified through transmetallation using a series of RE ions, including: La(III), Nd(III), Eu(III), Tb(III), Er(III), Tm(III), and Yb(III). In all cases, metal-exchange higher than 70 % was observed, with reproducible results. All transmetallated materials were fully characterized and compared to the parent MOF, Y-CU-10, in regards to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction (SCXRD) measurements were performed to provide further evidence of transmetallation occurring in the nonanuclear cluster nodes of the MOF. </div

A Step Towards Change: A Green Alternative for the Synthesis of Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are traditionally synthesized using formamide solvents that are hazardous to human health and the environment. In order to alleviate the environmental impact of MOF synthesis in both academic and industrial settings, safer and greener solvent alternatives are desired. Herein, STEPOSOL® MET-10U (N,N-dimethyl-9-decenamide), a bioderived solvent produced via olefin metathesis using renewable feedstocks, such as plant oils, is explored as a solvent for the synthesis of a series of structurally diverse MOFs

Modulating Photo- and Radioluminescence in Tb(III) Cluster-Based Metal–Organic Frameworks

Luminescent metal–organic frameworks (MOFs) are of interest for sensing, theranostics, dosimetry, and other applications. The use of lanthanoids in MOF metal nodes allows for intrinsic met-al-based luminescence. In this work, a facile route for modulat-ing the photoluminescent and radioluminescent properties of Tb(III)-based MOFs is reported. By using Tb(III)-cluster nodes as X-ray attenuators, and organic linkers with varying excited state energies as sensitizers, MOFs with metal-based, linker-based, and metal+linker-based photo- and radioluminescence are reported

Synthesis, characterization and photophysical properties of a new family of rare-earth cluster-based metal–organic frameworks

In this work, nine new rare-earth metal–organic frameworks (RE-MOFs, where RE = Lu(III), Yb(III), Tm(III), Er(III), Ho(III), Dy(III), Tb(III), Gd(III), and Eu(III)) isostructural to Zr-MOF-808 are synthesized, characterized, and studied regarding their photophysical properties. Materials with high crystallinity and surface area are obtained from a reproducible synthetic procedure that involves the use of two fluorinated modulators. At the same time, these new RE-MOFs display tunable photoluminescent properties due to efficient linker-to-metal energy transfer promoted by the antenna effect, resulting in a series of RE-MOFs displaying lanthanoid-based emissions spanning the visible and near-infrared regions of the electromagnetic spectrum