An ionothermally prepared S = 1/2 vanadium oxyfluoride kagome lattice.

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.

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework.

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.

A new chain structure: catena-poly[4,4'-(ethane-1,2-diyl)dipyridinium bis[[aquadifluoridooxidovanadate]-mu-fluorido]].

The title compound, {(C(12)H(12)N(2))[V(2)F(6)O(2)(H(2)O)(2)]}(n), features a novel extended-chain moiety, [VOF(2)F(2/2)(H(2)O)](n), comprising trans vertex-connected VOF(4)(H(2)O) octahedra. The octahedra themselves show the characteristic distortion due to the off-centering of the V(4+) ion, such that a short terminal V=O bond and an elongated trans V-OH(2) bond are present. Hydrogen bonding from the water molecules to terminal F atoms in adjacent chains generates associated chain dimers, which are loosely linked into sheets via additional hydrogen bonding involving the organic moieties. Structural relationships with previously described vanadium oxyfluoride species are briefly discussed.

Hydrothermal chemistry of oligomeric vanadium oxyfluorides.

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.

Hydrothermal vanadium fluoride chemistry: four new V3+ chain structures.

An exploratory study of the hydrothermal chemistry of vanadium in HF solutions has resulted in the preparation of four new vanadium (III) fluorides with chainlike structural motifs. [NH4]2[VF5] (1) and [C2N2H10][VF5] (2) feature infinite chains of trans corner-sharing VF4F2/2 octahedra, [C4N2H6][VF5].H2O (3) has cis corner-sharing [VF4F2/2]infinity chains, and [C10N2H8][VF3] (4) has trans corner-sharing [VF2F2/2]infinity chains bridged into sheets by the 4,4'-bipy linker. All four compounds exhibit antiferromagnetic behavior.

Novel vanadium(IV) oxyfluorides with 'spin-ladder'-like structures, and their relationship to (VO)2P2O7.

Three novel vanadium(IV) oxyfluorides have been prepared by hydrothermal synthesis. All three materials feature 'ladder'-like chains of edge- and corner-sharing V(O/F) octahedra, topologically similar to those in (VO)2P2O7. CsVOF3 and RbVOF3 are isostructural, whereas in (bpeH2)1/2[VOF3] (bpe = trans-1,2-bis(4-pyridyl)-ethylene) inclusion of the organic structure-directing agent affects both the conformation of the ladders and their packing within the unit cell. Magnetic susceptibility data for each of the new materials have been fitted using a spin-1/2 Heisenberg antiferromagnetic chain model, which shows that the predominant magnetic interactions act along the 'legs' of the ladder, with negligible interactions both along the 'rungs' and between neighboring chains. This behavior contrasts markedly with that of (VO)2P2O7 itself.