Dynamics and Kinetics of Structure Formation in Molecularly Tethered Fluorocarbon/Hydrocarbon Amphiphiles

作者:Elmahdy M M; Clark C G Jr; Butt H J; Muellen K; Floudas G*
来源:Journal of Physical Chemistry B, 2012, 116(46): 13812-13820.
DOI:10.1021/jp309465z

摘要

Biphasic fluorocarbon/hydrocarbon amphiphiles tethered to cores at distances commensurate with their packing requirement can provide thermodynamic pathways toward equilibrium. This contrasts with the analogous semifluorinated alkanes. The dynamics of a fluorous biphasic hexa(3,5-substituted-phenyl)benzene (HPB) is studied with dielectric spectroscopy as a function of temperature and pressure in comparison to the parent biphasic diphenylacetylene (DPA). Dielectric spectroscopy is a sensitive probe of the fluorocarbon environment through the end C-F dipole. Four dielectrically active processes were observed that associate with the CF3 environment within the different phases (isotropic, liquid-like lamellar, solid lamellar, glassy state). Pressure facilitates the construction of the equilibrium phase diagram. The kinetic pathways to fluorocarbon organization are explored by pressure-jumps experiments. A highly cooperative process was found that is atypical of a nucleation and growth process expected for first-order transitions.

  • 出版日期2012-11-22