Piezochromism in nickel salicylaldoximato complexes: tuning crystal-field splitting with high pressure.

The crystal structures of bis(3-fluoro-salicylaldoximato)nickel(II) and bis(3-methoxy-salicylaldoximato)nickel(II) have been determined at room temperature between ambient pressure and approximately 6 GPa. The principal effect of pressure is to reduce intermolecular contact distances. In the fluoro system molecules are stacked, and the Ni⋅⋅⋅Ni distance decreases from 3.19 Šat ambient pressure to 2.82 Šat 5.4 GPa. These data are similar to those observed in bis(dimethylglyoximato)nickel(II) over a similar pressure range, though contrary to that system, and in spite of their structural similarity, the salicyloximato does not become conducting at high pressure. Ni-ligand distances also shorten, on average by 0.017 and 0.011 Šfor the fluoro and methoxy complexes, respectively. Bond compression is small if the bond in question is directed towards an interstitial void. A band at 620 nm, which occurs in the visible spectrum of each derivative, can be assigned to a transition to an antibonding molecular orbital based on the metal 3d(x(2)-y(2)) orbital. Time-dependent density functional theory calculations show that the energy of this orbital is sensitive to pressure, increasing in energy as the Ni-ligand distances are compressed, and consequently increasing the energy of the transition. The resulting blueshift of the UV-visible band leads to piezochromism, and crystals of both complexes, which are green at ambient pressure, become red at 5 GPa.

Pressure-induced Pb-Pb bonding and phase transition in Pb2SnO4.

High-pressure single-crystal to 20 GPa and powder diffraction measurements to 50 GPa, show that the structure of Pb2SnO4 strongly distorts on compression with an elongation of one axis. A structural phase transition occurs between 10 GPa and 12 GPa, with a change of space group from Pbam to Pnam. The resistivity decreases by more than six orders of magnitude when pressure is increased from ambient conditions to 50 GPa. This insulator-to-semiconductor transition is accompanied by a reversible appearance change from transparent to opaque. Density functional theory-based calculations show that at ambient conditions the channels in the structure host the stereochemically-active Pb 6s2 lone electron pairs. On compression the lone electron pairs form bonds between Pb2+ ions. Also provided is an assignment of irreducible representations to the experimentally observed Raman bands.

Ionic liquids and deep eutectic mixtures as new solvents for the synthesis of vanadium fluorides and oxyfluorides.

An exploratory study of the synthesis of vanadium (oxy)fluorides (VOFs) using ionic liquids (ILs) and deep eutectic mixtures (DESs) as a solvent yielded 10 different materials. The previously reported chain type: (NH(4))(2)VF(5) (1), (NH(4))(2)VOF(4) (2), NH(4)VO(3) (3) and (H(2)NH(2)(CH(2))(2)NH(2))VF(5) (9) have been successfully produced for the first time using ILs as the reaction media. The monomeric (HNH(2)CH(3))(2)VOF(4)(H(2)O) (4), the dimer (HNH(2)CH(3))(4)V(2)O(2)F(8) (5) and the 1D chains (HNH(2)CH(3))(2)VF(5) (6), (H(2)O)(2)VF(3) (7), α-(H(2)NH(2)(CH(2))(2)NH(2))VOF(4) (8) and ß-(H(2)NH(2)(CH(2))(2)NH(2))VOF(4) (10) are novel materials. Template control has also been achieved by the selective choice of ILs or the appropriate deep eutectic mixture, where the expected template is delivered to the reaction by the partial breakdown of the urea derivative portion of the DES.

Solvothermal aluminophosphate zeotype synthesis with ionic liquid precursors.

We have carried out a study of aluminophosphate framework synthesis using several amine based ionic liquids and their parent amines as solvent and template. The results suggest that in the presence of fluoride ions from hydrofluoric acid the ionic liquids and their parent amines produce the same frameworks, while in synthesis without fluoride ions the products are not related. The results include the synthesis and crystal structure of a novel extra-large pore material using 1-methylpyrrolidine as solvent and template. The relationship between this and sodalite, which can be synthesised in cobalt aluminophosphate form using an ionic liquid prepared from 1-methylpyrrolidine is described. The crystal structures of two other new layered materials are also presented.

The use of ionic liquids in the synthesis of zinc imidazolate frameworks.

Four zinc imidazolate materials has been synthesized under ionothermal conditions using ionic liquids; [Zn(C2O4)(C3N2H4)], P21/a (1); [Zn(CH3COO)(C3N2H3)], Ima2 (2); [Zn4(C3N2H4)(C3N2H3)8], P (3) and [Zn(C3N2H3)2], I41 (4). Compounds 1 and 4 have already known structures, but have been synthesised for the first time using ionothermal methods. Compounds 2 and 3 are novel and have been synthesized for the first time in this work. The syntheses of 3 and 4 take place under almost exactly the same conditions, except that a lower synthesis temperature leads to a proportion of terminal imidazolate units in the structure of 3 while a slightly higher temperature leads to all bridging imidazolate units in 4.

Ionothermal synthesis of two novel metal organophosphonates.

Two novel metal phosphonates, Al(5)F(C(4)H(9)PO(3))(6)(OH)(2)(C(4)N(2)H(6))(2) and Ga(4)F(2)(C(4)H(9)PO(3))(8)H(5).(C(7)N(2)H(11)) have been prepared using an ionothermal approach and their structures solved using single-crystal X-ray diffraction. In , the breakdown of the ionic liquid solvent has occurred and a fragment of the cation coordinates to the aluminium in the structure. In , the ionic liquid cation acts as the template and is occluded. Compound is a chain structure while compound is molecular, unlike the vast majority of hydrothermally synthesised phosphonates, which are layered.

Ionothermal synthesis, structure and characterization of three-dimensional zinc phosphates.

The first metal phosphate analogue of the zeolite Na-J (framework type JBW) has been synthesized by an ionothermal approach along with zincophosphate thomsonite.

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework.

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of 'breathing' MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu2(OH)(C8H3O7S)(H2O)2H2O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.