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Item type:Publication, Access status: without files , Molecular dynamics of pyrene based discotic liquid crystals confined in nanopores probed by incoherent quasielastic neutron scattering(2014-10-28); ; ; ; Semiconducting nanowires made of discotic columnar liquid crystals can be obtained by impregnation into solid nanoporous templates, and provide new opportunities to tailor devices for organic electronics with promising charge carriers transport properties. These properties are tightly related to the self-assembly and molecular dynamics of the discotic columns inside the nanowires. We recently studied and rationalized the formation of different nanostructures in the columnar phase of pyrene derivative discotics nanoconfined in anodic alumina and porous silicon templates ([Cerclier et al., J. Phys. Chem. C, 2012, 116, 18990-18998, Kityk et al., Soft Matter, 2014, 10, 4522-4534]). We now present the molecular dynamics of nano-confined pyrene derivative mesogenic phases as studied by incoherent quasielastic neutron scattering over a broad range of correlation times. The combination of backscattering and time-of-flight techniques has allowed to describe the nature of the molecular motions at play on the pico to nanosecond time scale. The dynamics of the columnar phase is dominated by fluctuations of the lateral chains, while the onset of larger amplitude motions like whole-body reorientations and slow center-of-mass translational diffusion occurs at high temperature in the isotropic phase. Interestingly, nano-confinement does not qualitatively alter the nature of the molecular dynamics, but essentially blocks the long range translational motions and induces broader distributions of correlation times of the fastest local relaxations. This journal isPublicationtype: Journal Article44 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Thermotropic orientational order of discotic liquid crystals in nanochannels: An optical polarimetry study and a Landau-de Gennes analysis(2014-07-07); ; ; ; Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3-22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter. © The Royal Society of Chemistry 2014.Publicationtype: Journal Article33 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: without files , Structure and phase behavior of a discotic columnar liquid crystal confined in nanochannelsThe confinement of discotic columnar liquid crystal in nanoporous templates is a promising strategy to design nanofibers with potential applications in organic electronics. However, for many materials, geometric nanoconfinement has been shown to induce significant modifications of the physical properties, such as structure or phase behavior. We address the case of a discotic columnar liquid crystal confined in various templates. The influence of the size, the roughness, and the chemical nature of pores was investigated for a pyrene derivative by small-angle neutron scattering, X-ray diffraction, and calorimetry on a wide range of temperatures. A homeotropic anchoring (face-on orientation of the disk-shape molecules at the interface) is favored in all smooth cylindrical nanochannels of porous alumina while surface roughness of porous silicon promotes more disordered structures. The hexagonal columnar-isotropic phase transition is modified as a result of geometrical constraints and interfacial interactions.Publicationtype: Journal Article38