Remodelling a shp: Transmetalation in a Rare-Earth Cluster-Based Metal-Organic Framework.

Postsynthetic modification 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 transmetalation 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 transmetalated materials were fully characterized and compared to the parent MOF Y-CU-10 with regard to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction measurements were performed to provide further evidence of transmetalation occurring in the nonanuclear cluster nodes of the MOF.

Rare-earth metal-organic frameworks: from structure to applications.

In the past 30 years, metal-organic frameworks (MOFs) have garnered widespread attention owing to their diverse chemical structures, and tunable properties. As a result, MOFs are of interest for a wide variety of potential applications spanning multiple scientific and engineering disciplines. MOFs have been synthesized using several elements from the periodic table, including those with metal nodes containing s-, p-, d-, and f-block elements. MOFs synthesized with rare-earth (RE) elements, which include scandium, yttrium and the series of fifteen lanthanides are an intriguing family of MOFs from the standpoint of both structure and function. While RE-MOFs can possess many of the same properties common to all MOF families (i.e., permanent porosity, tunable pore size/shape, accessible Lewis acidic sites), they can also display unique structures and properties owing to the high coordination numbers and distinct optical properties of RE-elements. In this review, we present the progress, and highlight several discoveries from research conducted on the topic of RE-MOFs. First, diverse structures of RE-MOFs are presented, divided into classes based on the composition of the RE-metal node being RE(iii)-ions, RE(iii)-chains, or RE(iii)-clusters. Then, several potential applications of RE-MOFs are presented, highlighting examples in the areas of chemical sensing, white light emission, biological imaging, drug delivery, near infrared emission, catalysis, gas adsorption, and chemical separations.

Molecular Copper(I)-Copper(II) Photosensitizer-Catalyst Photoelectrode for Water Oxidation.

Copper(II)-based electrocatalysts for water oxidation in aqueous solution have been studied previously, but photodriving these systems still remains a challenge. In this work, a bis(diimine)copper(I)-based donor-chromophore-acceptor system is synthesized and applied as the light-harvesting component of a photoanode. This molecular assembly was integrated onto a zinc oxide nanowire surface, and upon photoexcitation, chronoamperometric studies reveal that the integrated triad can inject electrons directly into the conduction band of zinc oxide, generating oxidizing equivalents that are then transferred to a copper(II) water oxidation catalyst in aqueous solution, yielding O2 from water with a Faradaic efficiency of 76%.

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.

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.