On the structure of the Nx phase of symmetric dimers: inferences from NMR

NMR measurements on a selectively deuterated liquid crystal dimer CB-C9-CB, exhibiting two nematic phases, show that the molecules in the lower temperature nematic phase, NX, experience a chiral environment and are ordered about a uniformly oriented director throughout the macroscopic sample. The results are contrasted with previous interpretations that suggested a twist-bend spatial variation of the director. A structural picture is proposed wherein the molecules are packed into highly correlated chiral assemblies

The design and investigation of the self-assembly of dimers with two nematic phases

A series of non-symmetric dimers were synthesised containing either cyanobiphenyl or difluoroterphenyl moieties on one side and a range of long, short, bent, polar or apolar mesogens on the other side of the molecules. The dielectric anisotropy of the mesogens was varied systematically. The systems were characterised by differential scanning calorimetry (DSC), optical polarizing microscopy (OPM) and detailed X-ray diffraction (XRD) studies, both in the nematic and the Nx phase. The results are compared and structure properties relationships are discussed. A model for the assembly in the Nx phase is developed discussing Ntb structures, coaxial helices, swiss roll structures and chiral domain formation

The stabilisation of the Nx phase in mixtures

The phase behaviour of mixtures between two symmetric dimers, CBC9CB and the ether-linked analogue CBOC9OCB was investigated by Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD) studies. The dimeric constituents are fully miscible and the construction of a temperature-composition phase diagram reveals a surprising amplification of the stability of the Nx phase in compositions of up to 37 wt% of CBOC9OCB in CBC9CB. The origin for this enhancement of stability is discussed and an explanation based on chiral recognition is developed

NMR study of a bimesogenic liquid crystal with two nematic phases

Recent interest in bimesogenic liquid crystals showing two nematic phases has led us to investigate the nematic mean-field interactions in these nematic phases by using rigid solutes as probes. The nematic potential that is modelled by two independent Maier-Saupe terms is successful in fitting the observed dipolar couplings (order parameters) of para-, meta- and ortho-dichlorobenzene solutes in both the nematic phases of 39 wt% of 4-n-pentyl-4′-cyanobiphenyl (5CB) in α,ω-bis(4-4′-cyanobiphenyl)nonane (CB_C9_CB) to better than the 5% level. The derived liquid-crystal potential parameters G₁ and G₂ for each solute in the N and Ntb phases will be discussed. The most interesting observation is that G1 (associated with size and shape interactions) is almost constant in the Ntb phase, whereas G₂ (associated with longer-range electrostatic interactions) has large variation, even changing sign

Deuteron and proton NMR study of D₂, p-dichlorobenzene and 1,3,5-trichlorobenzene in bimesogenic liquid crystals with two nematic phases

The solutes dideuterium, 1,3,5-trichlorobenzene and p-dichlorobenzene (pdcb) are co-dissolved in a 61/39 wt% mixture of CBC9CB/5CB, a bimesogenic liquid crystal with two nematic phases. NMR spectra are collected for each solute. The local electric field gradient (FZZ) is obtained from the dideuterium spectrum. A double Maier-Saupe potential (MSMS) is used to rationalize the order parameters of pdcb. The liquid-crystal fields G₁ and G₂ are taken to be due to size and shape interactions and interactions between the solute molecular quadrupole and the mean FZZ of the medium. The FZZ’s obtained from D₂ and G₂ (from pdcb) are compared and discussed

Anomalous increase in nematic-isotropic transition temperature in dimer molecules induced by magnetic field

We have determined the nematic-isotropic transition temperature as a function of applied magnetic field in three different thermotropic liquid crystalline dimers. These molecules are comprised of two rigid calamitic moieties joined end to end by flexible spacers with odd numbers of methylene groups. They show an unprecedented magnetic field enhancement of nematic order in that the transition temperature is increased by up to 15K when subjected to 22T magnetic field. The increase is conjectured to be caused by a magnetic field-induced decrease of the average bend angle in the aliphatic spacers connecting the rigid mesogenic units of the dimers

A fibre forming smectic twist-bent liquid crystalline phase

We demonstrate the nanostructure and filament formation of a novel liquid crystal phase of a dimeric mesogen below the twist–bend nematic phase. The new fibre-forming phase is distinguished by a short-correlated smectic order combined with an additional nanoscale periodicity that is not associated with density modulation

Synthesis and photochromic properties of a bis(diarylethene)-naphthopyran hybrid

The synthesis and photochromic properties of a triphotochromic molecule consisting of one naphthopyran flanked by two diarylethene units investigated by UV-Visible and NMR spectroscopies are reported. Six different states resulting from the open/closed naphthopyran associated with one or two open/cyclized diarylethenes have been characterized. Switching of the naphthopyran group is possible, independently of the state of the diarylethene groups, permitting the controlled generation of electronically connected diarylethene groups. However, the diarylethene groups cannot be closed if the naphthopyran group is open

Molecular Hydrogen Formation on Low Temperature Surfaces in Temperature Programmed Desorption Experiments

The study of the formation of molecular hydrogen on low temperature surfaces is of interest both because it allows to explore elementary steps in the heterogeneous catalysis of a simple molecule and because of the applications in astrochemistry. Here we report results of experiments of molecular hydrogen formation on amorphous silicate surfaces using temperature-programmed desorption (TPD). In these experiments beams of H and D atoms are irradiated on the surface of an amorphous silicate sample. The desorption rate of HD molecules is monitored using a mass spectrometer during a subsequent TPD run. The results are analyzed using rate equations and the activation energies of the processes leading to molecular hydrogen formation are obtained from the TPD data. We show that a model based on a single isotope provides the correct results for the activation energies for diffusion and desorption of H atoms. These results can thus be used to evaluate the formation rate of H_2 on dust grains under the actual conditions present in interstellar clouds.Comment: 30 pages, 1 table, 6 figures. Published versio

Comparative analysis of anisotropic material properties of uniaxial nematics formed by flexible dimers and rod-like monomers

We report temperature dependencies of material properties such as dielectric anisotropy, birefringence, splay (K₁₁), twist (K₂₂), and bend (K₃₃) elastic constants of the uniaxial nematic (N) phase formed by flexible dimers of DTC5C9 and compare their behavior to that of a corresponding monomer MCT5. DTC5C9 forms a twist-bend nematic (Ntb) at temperatures below the N phase. Anisotropic properties of MCT5 are typical of the rod-like mesogens. In particular, birefringence increases as the temperature is reduced, following the classic behavior, described by Haller. The elastic constants also follow the standard behavior, with their ratios being practically temperature-independent. In contrast, DTC5C9 shows a dramatic departure from the standard case. Birefringence changes non-monotonously with temperature, decreasing on approaching the N-Ntb phase transition. K₃₃ decreases strongly to 0.4 pN near the N - Ntb transition, although remains finite. The ratios of the elastic constants in DTC5C9 show a strong temperature dependence that can be associated with the bend-induced changes in the orientational distribution function. The measured elastic properties are consistent with the tendency of the dimeric molecules to adopt bent configurations that give rise to the Ntb phase