Open Access

Show Abstract ▼

Abstract: A non-chiral ferroelectric nematic compound with a 1,3-dioxane unit in the mesogenic core called 2,3',4',5'-tetrafluoro-[1,1'-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) was studied by dielectric spectroscopy in the frequency range 0.1 Hz to 10 MHz over a wide range of temperatures. The compound exhibits three nematic phases on cooling from the isotropic phase, i.e., the ordinary paraelectric nematic N; the intermediate nematic NX and the ferroelectric NF phases. The least frequency process is due to the dynamics of ions. The middle frequency relaxation process P1 is like as observed in other ferronematic compounds and this mode is a continuation of the molecular flip-flop motion in the isotropic phase to the collective dynamics of dipoles which are strongly coupled with the splay fluctuations in nematic phases. In addition to this process, DIO shows an additional collective relaxation process P2 at higher frequencies both in the N and the NX phases. This mode originates from the polar/chiral molecules of the opposite chirality, these arise from the spontaneous symmetry breaking of achiral mesogens in the N phase. Both collective processes, P1 and P2, show soft mode-like characteristic behavior on cooling from the N to the NX-NF phase transition temperature and are shown to contribute independently to the formation of the ferronematic NF phase.

Show Abstract ▼

Abstract: High-resolution calorimetry has played a significant role in providing detailed information on phase transitions in liquid crystals. In particular, adiabatic scanning calorimetry (ASC), capable of providing simultaneous information on the temperature dependence of the specific enthalpy h ( T ) and on the specific heat capacity c p ( T ) , has proven to be an important tool to determine the order of transitions and render high-resolution information on pretransitional thermal behavior. Here we report on ASC results on the compound 2,3′,4′,5′-tetrafluoro[1,1′-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) and on mixtures with 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). Both compounds exhibit a low-temperature ferroelectric nematic phase ( N F ) and a high-temperature paraelectric nematic phase ( N ) . However, in DIO these two phases are separated by an intermediate phase ( N x ). From the detailed data of h ( T ) and c p ( T ) , we found that the intermediate phase was present in all the mixtures over the complete composition range, albeit with strongly decreasing temperature width for that phase with decreasing mole fraction of DIO ( x DIO ). The x DIO dependence on the transition temperatures for both transitions could be well described by a quadratic function. Both these transitions were weakly first order. The true latent heat of the N x − N transition of DIO was as low as L = 0.0075 ± 0.0005 J / g and L = 0.23 ± 0.03 J / g for the N F − N x transition, which is about twice the previously reported value of 0.115 J/g for the N F − N transition in RM734. In the mixtures both transition latent heats decrease gradually with decreasing x DIO . At all the N x − N transitions pretransition fluctuation effects are absent and these transitions are purely but very weakly first order. As in RM734 the transition from the N F to the higher-temperature phase exhibits substantial pretransitional behavior, in particular, in the high-temperature phase. Power-law analysis of c p ( T ) resulted in an effective critical exponent α = 0.88 ± 0.1 for DIO and this value decreased in the mixtures with decreasing x DIO toward α = 0.50 ± 0.05 reported for RM734. Ideal mixture analysis of the phase diagram was consistent with ideal mixture behavior provided the total transition enthalpy change was used in the analysis.

Open Access

Show Abstract ▼

Abstract: Polarized beam infrared (IR) spectroscopy provides valuable information on changes in the orientation of samples in nematic phases, especially on the role of intermolecular interactions in forming the periodically modulated twist–bent phase. Infrared absorbance measurements and quantum chemistry calculations based on the density functional theory (DFT) were performed to investigate the structure and how the molecules interact in the nematic (N) and twist–bend (NTB) phases of thioether dimers. The nematic twist–bend phase observed significant changes in the mean IR absorbance. On cooling, the transition from the N phase to the NTB phase was found to be accompanied by a marked decrease in absorbance for longitudinal dipoles. Then, with further cooling, the absorbance of the transverse dipoles increased, indicating that transverse dipoles became correlated in parallel. To investigate the influence of the closest neighbors, DFT calculations were performed. As a result of the optimization of the molecular cores system, we observed changes in the square of the transition dipoles, which well corresponds to absorbance changes observed in the IR spectra. Interactions of molecules dominated by pairing were observed, as well as the axial shift of the core to each other.

Show Abstract ▼

Abstract: We report the formation of a 3D body-centred self-assembled superlattice of gold nanoparticles whose interparticle gap, and hence its plasmonic properties, are adjustable exclusively in the xy -plane. Thus, even though the particles are spherical, their anisotropic packing generates tailorable plasmonic dichroism. The gold nanoparticles are coated with forked ligands containing two mesogens: either two cholesterols (“twin”), one cholesterol and one azobenzene (“Janus”), or a mixture of the two. Beside the body-centered arrangement of gold nanoparticles, the structure also contains unusual two-dimensionally modulated smectic-like layers of mesogens in an egg-box geometry. Moreover, the presence of azobenzene mesogens allows the superlattice to be melted through UV-induced photo-isomerization; the process is reversible displaying low fatigue on repeated cycling.

Open Access

Show Abstract ▼

Abstract: Gold nanoparticles (AuNPs) have been prepared and surface-functionalized with a mixture of 1-hexanethiol co-ligands and chiral discogen ligands separated from a disulfide function via a flexible spacer. Polarized optical microscopy together with differential scanning calorimetry showed that the organic corona of the nanocomposite forms a stable chiral discotic nematic image file: d0sc05100d-t1.tif phase with a wide thermal range. Synchrotron X-ray diffraction showed that gold NPs form a superlattice with p2 plane symmetry. Analysis indicated that the organic corona takes up the shape of a flexible macrodisk. Synchrotron radiation-based circular dichroism signals of thin films are significantly enhanced on the isotropic-LC transition, in line with the formation of a chiral nematic phase of the organic corona. At lower temperatures the appearance of CD signals at longer wavelengths is associated with the chiral organisation of the NPs and is indicative of the formation of a second helical structure. The decreased volume required and the chiral environment of the disc ligands drives the nanoparticles into columns that arrange helically, parallel to the shortest axis of the two dimensional lattice.