Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by ¹H, ²H, and ¹³C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.     

HREM studies of the structure and the oxidation process of copper clusters created by inert gas aggregation

Structure and reactivity with oxigen of Cu clusters in the size range of 4.5±2.5 nm created by the inert gas aggregation technique were studied by HREM. The pure Cu clusters investigated under clean conditions show the structures of MTP's with a small lattice dilatation of the (111) plane of 1.25%. For icosahedral and decahedral particles this dilatation corresponds to a splitting of the nearest neighbour distance showing two different values, i.e. dilatation of 2.2% and contraction of 2.8% for the two edges of the deformed tetrahedral subunits, respectively. Oxidation at room temperature and air pressure of 1 bar only begins after a few minutes of exposure to air, after having undergone creation of probably non-stoichiometric intermediate states in the cuprite Cu₂O structure with the bulk values of the bond lengths.     

Phase dynamics of a detuned single-mode laser

We report measurements on the phase dynamics of a detuned single mode laser which has in the past shown correspondence to the complex Lorenz equation. The corresponding ranges of periodic pulsing, of detuned chaos and of windows within the chaotic domain are investigated.Invited paper     

Ab initio path-integral molecular dynamics

A path-integral molecular dynamics technique for strongly interacting atoms using ab initio potentials derived from density functional theory is implemented. This allows the efficient inclusion of nuclear quantum dispersion in ab initio simulations at finite temperatures. We present an application to the quantum cluster H ₅ ⁺ .     

Liquid crystalline behaviour from binary mixtures of non-mesogenic 4-alkyl-N-(4-cyanophenyl) piperidines [1]

A relatively rare phenomenon, the induction of thermotropic mesophases from combinations of homologues of non-mesogenic compounds, is examined in some detail. Thus, monotropic nematic phases have been obtained from binary mixtures of 4-alkyl-N-(4-cyanophenyl)piperidines (I). Except for the hexyl homologue, the compounds I with butyl to nonyl as alkyl groups are non-mesomorphic as neat materials. From phase diagrams, the nematic clearing temperatures of the binary mixtures are found to vary linearly with composition and to increase as the molecular lengths of the components are increased. By introducing a methyl group at the 1-position of the alkyl chain, the melting points of the neat components are depressed, and the nematic clearing temperatures of the binary mixtures are lowered. Factors associated with the induction of this mesomorphism and with the 'kinetic' and thermodynamic stabilities of the monotropic nematic phases are discussed. Among these is the orientation between the rings of the core groups in I and in the more common mesogens, the trans-4-alkyl-1-(4-cyanophenyl) cyclohexanes, II.     

Smectic liquid-crystalline phases of F(CF2)7(CHOH)(CH2)8H and F(CF2)9(CHOH)(CH2)10H Comparison with other partially fluorinated molecules

Partially fluorinated alcohols F(CF₂)_m(CHOH)(CH₂)_nH (where m = 7, n = 8 and m = 9, n = 10) exhibit highly ordered smectic liquid-crystalline phases, as confirmed by optical microscopy and differential scanning calorimetry. Miscibility studies show that the smectic phases of the two alcohols are not of the same type. The related partially fluorinated ketones F(CF₂)_mCO(CH₂)_nH do not form a detectable mesophase. This is rather surprising since the (more polar) corresponding alcohols and the (less polar) analogous iodides and n-alkanes do. A brief discussion of the results and a comparison among partially fluorinated alkanes with various functional groups are presented.