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- Molecular dynamics in tilted bilayer smectic phases: a proton nuclear magnetic resonance relaxometry studyPublication . Carvalho, A.; Sebastião, P. J.; Ribeiro, A. C.; Nguyen, H. T.; Vilfan, M.A proton nuclear magnetic resonance (NMR) relaxation study of molecular dynamics in the liquid crystal 4-octylphenyl 2-chloro-4-(4-cyanobenzoyloxy)benzoate (DB8Cl) is presented. DB8Cl molecules possess a strong polar terminal group and form, in addition to the nematic phase, three different smectic phases: bilayer smectic A, bilayer smectic C, and anticliniclike smectic C phase. The proton spin-lattice relaxation times were measured in all mesophases over a broad frequency range of six decades by applying conventional and fast field-cycling NMR techniques. The parameters obtained in the analysis of the experimental data give quantitative information on molecular motions, particularly for the tilted smectic phases of DB8Cl. In contrast to former conjectures, we found that the low-frequency relaxation in the bilayer smectic C phases results from director fluctuations about the layer normal, which occur without distortion of the layers, and from layer undulations, similar to those in the smectic A phase. In the low-temperature bilayer smectic C phase, a considerable slowing-down of molecular translational diffusion is observed. It confirms indirectly the anticlinic character of this mesophase. Measurements of angular dependence of the relaxation times at 60 MHz support the conclusions obtained from the frequency dispersion data.
- Diffuse reflectance studies of β-phenylpropiophenone and benzophenone inclusion complexes with calix[4], [6] and [8]arenesPublication . Ferreira, Luís F. Vieira; Ferreira, Margarida R. Vieira; Oliveira, Anabela S.; Branco, T. J. F.; Prata, José V.; Moreira, J. C.The formation of inclusion complexes of β-phenylpropiophenone and benzophenone with p-tert-butylcalix[4], [6] and [8]arenes (powdered solid samples) was studied with the use of diffuse reflectance techniques. Experimental evidence was obtained for inclusion in all cases. The benzophenone n → π* absorption band exhibits hypsochromic shifts with an increase of the calixarene ring aperture, providing evidence for an increase in cavity polarity. β-Phenylpropiophenone exhibits strong room temperature phosphorescence in contrast to its solution behaviour, and this is a clear evidence for the inclusion of this probe within the calixarene molecules. Calix[4]arene and calix[8]arene provide a more rigid environment to β-phenylpropiophenone whereas calix[6]arene appears to be more flexible. Transient absorption spectra of inclusion complexes with benzophenone (1 : 1 mol : mol, excited at 355 nm) show major triplet formation in the calix[4]arene case, while the ketyl radical of benzophenone is formed in the calix[6]arene case and is predominant in the calix[8]arene case. Phenoxyl radical transient absorption also becomes evident in the last two cases. For β-phenylpropiophenone (1 : 1 mol : mol) phenoxyl radicals are formed but no evidence was found for triplet or ketyl radical formation of this ketone in the calix[4]arene case. However, strong support for the ketyl radical of the aryl alkyl ketone was found for calix[6]arene and calix[8]arene inclusion complexes.