A family of homeotypic porous lanthanide metal−organic frameworks (MOFs), [Ln(btc)(H2O)]·guest (Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Ho (6), Er (7), and Yb (8); guest: DMF or H2O) was synthesized. The structures of the as-synthesized compounds are tetragonal and contain 1D channels with accessible lanthanide ions. In situ single crystal X-ray diffraction shows that 1 undergoes a single-crystal to polycrystalline to single-crystal transformation from room temperature to 180 °C. During the release of DMF and water molecules from the channels by evacuation and subsequent heating, the structures of 1 and 7 transformed from tetragonal to monoclinic, and then to tetragonal, while the structure of 8 remained tetragonal. The transformation between the monoclinic and the low temperature tetragonal phases is reversible. The Ln(btc) MOFs are stable to at least 480 °C and are among the most thermally stable MOFs. The Ln(btc) MOFs act as efficient Lewis acid catalysts for the cyanosilylation of aldehydes yielding cyanohydrins in high yields within short reaction times. 1 also catalyzes the cyanosilylation of less reactive substrates, such as ketones at room temperature. The Ln(btc) MOFs could be recycled and reused without loss of their crystallinity and activity.

Palladium nanoparticles have been immobilized into an amino-functionalized metal–organic framework (MOF), MIL-101Cr-NH 2 , to form Pd@MIL-101Cr-NH 2 . Four materials with different loadings of palladium have been prepared (denoted as 4-, 8-, 12-, and 16 wt %Pd@MIL-101Cr-NH 2 ). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), N 2 -sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL-101Cr-NH 2 , electron tomography was employed to reconstruct the 3D volume of 8 wt %Pd@MIL-101Cr-NH 2 particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high-energy X-rays (60 keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki–Miyaura cross-coupling reaction. The best catalytic performance was obtained with the MOF that contained 8 wt % palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6 nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15 mol %). The material can be recycled at least 10 times without alteration of its catalytic properties.

A ruthenium trichloride complex has been loaded into an aluminium metal-organic framework (MOF), MOF-253, by post-synthetic modification to give MOF-253-Ru. MOF-253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF-253-Ru was characterised by elemental analysis, N(2) sorption and X-ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post-synthetic modification and used as a heterogeneous catalyst. MOF-253-Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)(2) as the oxidant under very mild reaction conditions (ambient temperature to 40 °C). High conversions (up to >99%) were achieved in short reaction times (1-3 h) by using low catalyst loadings (0.5 mol% Ru). In addition, high selectivities (>90%) for aldehydes were obtained at room temperature. MOF-253-Ru can be recycled up to six times with only a moderate decrease in substrate conversion.

We report a new open-framework silicogermanate SU-61 containing 26-ring channels with a low framework density. It can be seen as a crystalline analogue to the mesoporous silica MCM-41. The structure is built from the assembly of (Ge,Si)10(O,OH)28 clusters. It is the first time that silicon has been successfully introduced in the Ge10 cluster in significant amounts ( approximately 21% of the tetrahedral sites). Five- and six-coordinated Ge10 clusters have previously been observed in other germanate compounds leading to either dense or open structures. In SU-61, the seven-coordinated clusters fall onto yet another underlying net, the osf net. SU-61, along with other Ge10 based frameworks, shows the versatility of the germanate system to adopt defined topologies playing on the connectivity of the clusters following the principles of net decoration and scale chemistry.