A family of five hybrid ABX perovskites has been synthesized using hypophosphite (HPOO) as the X-site ion. These compounds adopt the general formula [Am]Mn(HPOO), where Am = guanidinium (GUA), formamidinium (FA), imidazolium, triazolium, and dabconium. We explore the diverse structural and phase transition behavior of these materials through single-crystal diffraction measurements and demonstrate contrasting magnetism in two of the phases, Am = GUA and FA, that arises from structural distortions. The results show that hypophosphite perovskites offer a promising platform for generating new functional materials.

Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600 °C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 °C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

Following the recent discovery of the [A]Mn(H2POO)3 (H2POO- = hypophosphite) perovskite family, we report the A = [NH2(CH3)2]+ (dimethylammonium, DMA) member. This phase shows an unusually large unit cell due to the position of the A-site cation within the perovskite cage windows rather than the centre, as is the norm. We discuss the tendency of the hypophosphite perovskite skeleton to accommodate differently shaped A-site cations through the generation of unconventional tilts and columnar shifts, then enumerate these tilts and shifts for all known [A]Mn(H2POO)3 phases.