High Reactivity of Metal-Organic Frameworks under Grinding Conditions: Parallels with Organic Molecular Materials

Interconversion made easy: Metal–organic frameworks (MOFs) are surprisingly reactive under grinding conditions and can perform various rearrangements (see picture). In this respect, the results reveal clear parallels between MOFs and organic molecular materials.

A metal complex that imitates a micelle

A metal complex with a micelle-like, core-shell structure adopts higher nuclearity in water than in organic solvents, thereby imitating also the growth of a micelle, but through covalent rather than non-covalent aggregation.

Ionic liquid S-alkylthiouronium salts

The prepn. and characterization of a series of ionic liqs. based on S-alkylthiouronium cations prepd. from thiourea, 1,3-dimethylthiourea, 1,3-diethylthiourea and 1,3-tetramethylthiourea coupled with bis{(trifluoromethane)sulfonyl}imide, bromide, methylsulfate or ethylsulfate anions are reported. All are liqs. at room temp. or solids with m.ps. close to room temp., except for the bromide salts, which have m.ps. below 92 °C. Systematic variation in the N- and S-alkyl substituents demonstrates how the phys. properties of these ionic liqs. can be readily controlled. The mutual miscibility limits of representative examples with octane, dodecane and toluene have been detd. as a function of temp., and the extn. of dibenzothiophene from dodecane as a model for desulfurisation of diesel has been investigated.

A stereocontrolled method for the synthesis of D- and L-2-deoxy-C-nucleosides using an intramolecular Sakurai-type cyclisation reaction

A novel synthetic procedure has been developed that provides access to D/L-2-deoxy-C-nucleosides from 3,4-epoxytetrahydrofuran in seven steps and in moderate to good yields. The key chemical transformation was the Lewis acid catalysed intramolecular cyclisation reaction of an acetal for which the stereochemical outcome was dependent of the reagents' ratio.

From PASS 1 to YES to AND logic: building parallel processing into molecular logic gates by sequential addition of receptors

The synthesis and photophysical characterization of a novel molecular logic gate 4, operating in water, is demonstrated based on the competition between. fluorescence and photoinduced electron transfer (PET). It is constructed according to a 'fluorophore-spacer-receptor(1)-spacer-receptor(2)' format where anthracene is the. fluorophore, receptor(1) is a tertiary amine and receptor(2) is a phenyliminodiacetate ligand. Using only protons and zinc cations as the chemical inputs and. fluorescence as the output, 4 is demonstrated to be both a two-input AND and INH logic gate. When 4 is examined in context to the YES logic gates 1 and 2, and the two-input AND logic gate 3 and three-input AND logic gate 5, each with one or more of the following receptors including a tertiary amine, phenyliminodiacetate or benzo-15-crown-5 ether, logic gate 4 is the missing link in the homologous series. Collectively, the molecular logic gates 1-5 corroborate the PET 'fluorophore-spacer-receptor' model using chemical inputs and a light-signal output and provide insight into controlling the. fluorescence quantum yield of future PET-based molecular logic gates.

Highly selective and efficient hydrogenation of carboxylic acids to alcohols using titania supported Pt catalysts

Selective hydrogenation of carboxylic acids to alcohols and alkanes has been achieved under remarkably mild reaction temperatures and H-2 pressures (333 K, 0.5 MPa) using Pt/TiO2 catalyst.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Functionalised ionic liquids: synthesis of ionic liquids with tethered basic groups and their use in Heck and Knoevenagel reactions

A simple and efficient synthesis of a novel series of ionic liquids bearing nucleophilic (Me2N) and non-nucleophilic base ((Pr2N)-Pr-i) functionalities is described. The non-nucleophilic base functionality resembles the structure of the Hunig's base (N, N-diisopropylethylamine), which has been used widely in organic synthesis. A qualitative measure of the basicity of these ionic liquids is presented by utilising their interaction with universal indicator. The basicity of these ionic liquids was found to be dependent on the amine tether and choice of linker between the two nitrogen centres. The relative base strength of these ionic liquids was also probed by using them as catalysts in the Heck and Knoevenagel reactions.

Synthesis and Reactions of Enantiopure Substituted Benzene cis-Hexahydro-1,2-diols

Enantiopure cis-dihydro-1,2-diol metabolites, obtained from toluene dioxygenase-catalysed cis-dihydroxylation of six monosubstituted benzene substrates, have been converted to their corresponding cis-hexahydro-12-diol derivatives by catalytic hydrogenation via their cis-tetrahydro-1,2-diol intermediates. Optimal reaction conditions for total catalytic hydrogenation of the cis-dihydro-1,2-diols have been established using six heterogeneous catalysts. The relative and absolute configurations of the resulting benzene cis-hexahydro-1,2-diol products have been unequivocally established by X-ray crystallography and NMR spectroscopy. Methods have been developed to obtain enantiopure cis-hexahydro-1,2-diol diastereoisomers, to desymmetrise a meso-cis-hexahydro-1,2-diol and to synthesise 2-substituted cyclohexanols. The potential of these enantiopure cyclohexanols as chiral reagents was briefly evaluated through their application in the synthesis of two enantiomerically enriched phosphine oxides from the corresponding racemic phosphine precursors.