We present an ionothermal-based method for the simple and low-cost enrichment in 17 O of oxide materials. This is demonstrated for the case of SIZ-4, an ionothermally-prepared aluminophosphate framework with the CHA topology. A preliminary study of unenriched samples of SIZ-4 highlights the importance of the careful choice of template in order to obtain an ordered structure. We then show how an ionothermal synthesis procedure incorporating microlitre quantities of 17 O-enriched H 2 O enables asprepared and calcined samples of SIZ-4 to be obtained with 17 O enrichment levels that are sufficient to enable the recording of high-quality 17 O solid-state NMR spectra. While second-order quadrupolarbroadened resonances are unresolved in 17 O MAS NMR spectra, 17 O double-rotation (DOR) and multiple-quantum (MQ)MAS NMR spectra reveal distinct resonances that are partially assigned by comparison with NMR parameters derived using first-principles calculations. The calculations also enable an investigation of the dependence of 17 O NMR parameters on the local structural environment. We find that both the 17 O isotropic chemical shift and quadrupolar coupling constant show clear dependencies on Al-O-P bond lengths, and angles and will therefore provide a sensitive probe of structure and geometry in aluminophosphate frameworks in future studies.
Frustrated magnetic lattices offer the possibility of many exotic ground states that are of great fundamental importance. Of particular significance is the hunt for frustrated spin-1/2 networks as candidates for quantum spin liquids, which would have exciting and unusual magnetic properties at low temperatures. The few reported candidate materials have all been based on d(9) ions. Here, we report the ionothermal synthesis of [NH(4)](2)[C(7)H(14)N][V(7)O(6)F(18)], an inorganic-organic hybrid solid that contains a S = 1/2 kagome network of d(1) V(4+) ions. The compound exhibits a high degree of magnetic frustration, with significant antiferromagnetic interactions but no long-range magnetic order or spin-freezing above 2 K, and appears to be an excellent candidate for realizing a quantum spin liquid ground state in a spin-1/2 kagome network.
Hydrogen sulfide is an extremely toxic gas that is also of great interest for biological applications when delivered in the correct amount and at the desired rate. Here we show that the highly porous metal-organic frameworks with the CPO-27 structure can bind the hydrogen sulfide relatively strongly, allowing the storage of the gas for at least several months. Delivered gas is biologically active in preliminary vasodilation studies of porcine arteries, and the structure of the hydrogen sulfide molecules inside the framework has been elucidated using a combination of powder X-ray diffraction and pair distribution function analysis.
Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.
Nine new vanadium oxyfluorides, containing ten different oligomeric vanadium (oxy)fluoride anions have been prepared by solvothermal synthesis in water-ethylene glycol and using organic cations as co-crystallising agents. Crystal structures are reported for each. Amongst the ten structure types, five represent previously unobserved moieties, including one monomeric unit (cis-[VOF4(H2O)]2-), two dimers ([V2O2F6(H2O)2]2- and [V2O2F8]4-) and two tetramers (both isomers of composition [V4O4F14]6-). Structural relationships between the various units are discussed, together with some rationalisation of their occurrence as a function of synthetic variables.
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