Crystal and molecular structure of two isomeric N-methyl iodides of thiobinupharidine:trans,trans-N,N′-dmethyl-thiobinupharidine diiodide dihydrate acetone solvate andcis,trans-N,N′-dimethylthiobinupharidine diiodide dihydrate methanol solvate

The crystal structures of two quaternary salts,trans,trans- andcis,trans-N,N-dimethylthiobinupharidine diiodide, whose stereochemistries have been previously characterized by¹³C NMR spectroscopy, have now been determined by X-ray analysis. Differences in the nitrogen atom configuration of the AB quinolizidine fragment result in different conformations of the central part of the cations, the spiro tetrahydrothiophene ring, and specific selectivity toward solvent molecules. Thetrans,trans isomer crystals obtained from an acetone/methanol/water solution contained two water and one acetone molecule, while thecis,trans cocrystallized from the same solvent mixture with methanol and two water molecules. Very weak hydrogen bonds of the C-HI^– type determine interactions between the quaternary cations and the I^– anions in the solid state. Water molecules form a dimer, and this dimer is hydrogen bonded to the I^– anions. Organic solvent molecules included in crystals show different type of interactions with surrounding molecules: (i) the acetone molecule is trapped in the cavity of thetrans,trans cation by very weak C-HO interactions; (ii) methanol is hydrogen bonded to a water molecule while with thecis,trans cation and I^– anion interacts only by van der Waals forces.     

Critical examination of the supermolecule density functional theory calculations of intermolecular interactions

The results of calculations employing twelve different combinations of exchange and correlation functionals are compared with results of ab initio calculations for two different configurations of the water dimer and three different configurations of the thymine-adenine complex. None of the density functional theory (DFT) treatments could properly reproduce the results of coupled-cluster calculations for all configurations examined. The DFT approaches perform well when the interaction energy is dominated by the electrostatic component and the dispersion energy is less important. Two mechanisms that compensate for the missing dispersion component were identified. The first one is the decrease of the magnitude of the intermolecular exchange-repulsion and the second one is the increase of the magnitude of the attractive deformation energy. For some functionals both effects are observed together, but for some other ones only the second effect occurs. The three correlation functionals that were examined were found to make only very small contributions to the deformation energy. The examination of angular and distance dependence of the interactions shows that the currently available DFT approaches are not suitable for developing intermolecular potential energy surfaces. They could however be used to find global minima on potential energy surfaces governed by intermolecular electrostatic interactions. Additional single point ab initio calculations are recommended as the means of validating optimized structures.     

The origin of deficiency of the supermolecule second-order Moller-Plesset approach for evaluating interaction energies

Calculations for the complex of thymine and adenine are used to show that the supermolecule second-order Moller-Plesset perturbation theory (MP2) approach for evaluating interaction energies fails in certain cases because of the behavior of one of its components: the uncoupled Hartree-Fock dispersion energy. A simple approach for correcting the MP2 supermolecule interaction energies is proposed. It focuses on correcting a relatively small difference between the MP2 and coupled cluster interaction energies, which is a very appealing feature of the new approach considering a benchmark role played by coupled cluster results.     

Electrical and Photoelectrical Properties of n-CuInS2 Single Crystals

The temperature dependences of free electron density and mobility in n-CuInS₂ single crystals have been determined from the Hall effect measurements. The ionization energy of donors and their densities have been estimated. The results of measurements show that the crystals are strongly compensated. The spectral distribution of photoconductivity, the dependence of photoconductivity on excitation intensity, and the photoconductivity decay with time have been measured in the n-CuInS₂ crystals at different temperatures. The results of photo-conductivity measurements suggest linear recombination of photo-electrons at weak excitation and quadratic recombination at high excitation intensity. The compensated deep acceptor probably acts as the recombination centre.     

N-Chlorophthalimide as a mild and efficient chlorination reagent in the Gassman ortho alkylation of aromatic amines. Synthesis of 3-(methylthio)oxindoles

A practical modification of the Gassman 3-(methylthio)oxindole synthesis is reported. In our method, substituted anilines and 2-(methylthio)acetamide were reacted under mild reaction conditions, in the presence of N-chlorophthalimide as a chlorinating agent to give α-amidosulfides, which, in the next step of the process, were cyclized to give 3-(methylthio)oxindoles. The method was successfully applied for the synthesis of the key intermediate, 2-(2-amino-3-benzoylphenyl)-2-(methylthio)acetamide, in the process of the preparation of nepafenac, a commonly used ophthalmic drug.     

Synthesis of fullerene derivatives

This paper presents the results of plasmochemical synthesis of fullerene derivatives with hydrogen, iodine, iridium, platinum, and scandium. The synthesis is carried out under atmospheric pressure in a carbon-helium plasma stream formed by an ac arc in the rf range.     

Long-alkyl-chain quaternary ammonium lactate based ionic liquids

A new group of quaternary ammonium lactate based ionic liquids have been prepared and characterized. Didecyldimethylammonium (DDA) and benzalkonium (BA) D,L- and L-lactates are air-stable, hydrophilic, surface-active salts. They are very effective antibacterial and antifungal agents, especially the DDA lactates, against Streptococcus mutants and Candida albicans. Their activities are comparable or more effective than the original benzalkonium chloride. In addition, they have been shown to be good insect-feeding deterrents. However, they are poor antifungal agents for wood preservation. The toxicity of the DDA and BA lactates has also been studied and the results are presented in this paper.     

Ab initio ground- and excited-state intermolecular potential energy surfaces for the NO-Ne and NO-Ar van der Waals complexes

The ground- [NO(X(2)Π)] and excited-state [NO(A(2)Σ(+))] intermolecular potential energy surfaces (IPESs) of the NO-Ne and NO-Ar van der Waals complexes are evaluated using the RCCSD(T) spin-restricted coupled cluster method and d-aug-cc-pVQZ basis set extended with a set of 3s3p2d1f1g midbond functions. These bases are selected from the results of a systematic basis-set convergence study carried out for the NO(A(2)Σ(+))-Ar state. We fit the interaction energies to analytic functions and compare the results to those previously available. The NO-Ar (NO-Ne) IPESs are characterized by absolute minima of -120 and -75 cm(-1) (-58 and -5 cm(-1)) at the ground and first excited state, respectively, located close to the T-shaped geometries for the ground states and at linear dispositions in the case of the excited states. The potentials are further used in the evaluation of the rovibrational spectra of the complexes, and the results are compared to those available in the literature.