Hydrogenation of

The course of the hydrogenation of [5]- and [6]metacyclophane (1b and 1c) and their thermochemistry is described. Both compounds are hydrogenated rapidly (within 10 s) to furnish the bridgehead olefins 13b and 12c. The accompanying hydrogenation enthalpies are -220 and -141 kJmol(-1), respectively. Strain energies (SE) and olefinic strains (OS) of a number of bridgehead olefins have been evaluated by DFT calculations; it was concluded that 13b belongs to the class of hyperstable olefins which correlates nicely with its reluctance to undergo hydrogenation. By combining experimental hydrogenation enthalpies and DFT calculations, SE of 187 and 121 kJmol(-1) were derived for 1b and 1c.     

Surface-induced ordering in thin uniaxial liquid crystal films

The interface localization transition in thin uniaxial liquid crystal films with competing surface fields has been studied using Metropolis Monte Carlo simulations. The model is constructed from a lattice of continuously orientable interacting spins, and the Hamiltonian contains both bilinear and biquadratic contributions. The biquadratic contribution to the Hamiltonian is familiar from the Lebwohl-Lasher model, and accounts for the particle anisotropy in a liquid crystal. The head-tail asymmetry of the molecules in a uniaxial liquid crystal is taken into account through a bilinear contribution familiar from the classical ferromagnetic Heisenberg model with exchange anisotropy Lambda. The critical temperature T(c), characterizing the interface localization transition within the uniaxial liquid crystal film, depends strongly on the relative magnitudes of the bilinear and biquadratic interactions between the spins. For systems dominated by the biquadratic interaction, T(c) is found to be close to the bulk critical temperature of the system. But as the biquadratic interaction strength is reduced, T(c) departs markedly from the bulk critical temperature of the system.