On the ordering in [(C2H5)4N]2CuCl4 crystal: an X-ray study and theoretical considerations

The crystal structure [(C₂H₅)₄N]₂CuCl₄ has been determined by X-ray diffraction at 243K. The room temperature phase (phase I) belongs to the space group P4₂/nm [1] whereas the low temperature phase (phase II) is orthorhombic and belongs to the space group Pnna. The phase transition at T_c=258K is of improper ferroelastic type and it is associated with the ordering of the CuCl₄ ^2? and a partial ordering of the [(C₂H₅)₄N]⁺ ions which are disordered in the high temperature tetragonal phase. At lower temperature, there occurs another instability which could correspond to a complete ordering in the crystal.     

Absorbance spectra of polycrystalline samples and twinned crystals of oligothiophenes

We propose optical absorption technique at oblique incidence as one of the spectroscopic tools that allow experimentally recognizing the macroscopic order and structural features of molecular solids of conjugated molecules, from single crystals to polycrystalline or twinned samples. We apply this spectroscopy to quaterthiophene as representative of a wide class of materials that usually possess optical transitions of Frenkel exciton origin with strong directional dispersion. The comparison between experimental and simulated data gives evidence of the high sensitivity of this technique for determining quantitatively the polycrystallinity of the measured samples, whose domains may show mirror-like orientation of the unit cell with respect to one of its faces.Frenkel exciton; Oligothiophene, Optical properties     

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton-Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF₄)₂. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF₄)₂ by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF₄) regenerates protonated complex [ 1 ](BF₄)₂. In presence of acetic acid in acetonitrile solvent [ 1 ](BF₄)₂ shows electrocatalytic proton reduction with a k_obs of ≈200 s⁻¹ at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a Co^II−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.     

Hydrothermal synthesis of fluorated single crystals: BaMnF4 and BaF2·HF

Investigations to eliminate defects in the incommensurate phase BaMnF₄, led to a method of preparation at a temperature lower than the melting point of BaMnF₄. Qualitative studies of the systems BaF₂ -H₂O -HF and MnF₂ -H₂O -HF showed that very pure single crystals of BaMnF₄ could be grown at a temperature lower than 300°C. Several new phases could be isolated as single crystals, in particular: BaF_2^′HFSingle crystal X-ray analysis revealed the compound to be monoclinic (Space Group P2₁ and Z = 2) and confirmed the formula found by chemical analysis. However, because of the difficulty to distinguish between fluorine and oxygen atoms, some problems remain, which will be solved by neutron diffraction studies. Infrared analysis indicate the presence of HF^?₂ and suggest the following representation: (Ba²⁺)₂(HF^?₂)₂(F^?)₂.It is possible to extend this method of synthesis to the preparation of other fluorides and related compounds, in particular to those of europium and strontium.     

CO(2) concentration measurements on air samples by mass spectrometry

A new technique for measuring CO(2) concentration in air samples, based on mass spectrometry, is described as an alternative to the common gas chromatographic method. Using a dual inlet isotope ratio mass spectrometer (IRMS), the ratio of the abundances of the m/z peaks 44 and 28 is determined. The precision of measurements (standard deviation <3 ppmv) is generally as good as the analysis with gas chromatography for small air samples (<1 ml STP of air). A major advantage of this new method is the possibility of parallel elemental and isotopic measurements of many air components. The technique is further improved by new wide mass range mass spectrometers allowing simultaneous intensity measurements of several m/z values between 28 and 44, resulting in an uncertainty of <0.5 ppm. The precision is somewhat limited by the production of N(2)O and NO(2) from N(2) and O(2) in the ion source, which accounts for about half of the signal strength at m/z 44. Copyright 2000 John Wiley & Sons, Ltd.