Exploring the Impact of Intermolecular Interactions on the Glassy Phase Formation of Twist-Bend Liquid Crystal Dimers: Insights from Dielectric Studies.

The formation of the nematic to twist-bend nematic (NTB) phase has emerged as a fascinating phenomenon in the field of supramolecular chemistry, based on complex intermolecular interactions. Through a careful analysis of molecular structures and dynamics, we elucidate how these intermolecular interactions drive the complex twist-bend modulation observed in the NTB. The study employs broadband dielectric spectroscopy spanning frequencies from 10 to 2 × 109 Hz to investigate the molecular orientational dynamics within the glass-forming thioether-linked cyanobiphenyl liquid crystal dimers, namely, CBSC7SCB and CBSC7OCB. The experimental findings align with theoretical expectations, revealing the presence of two distinct relaxation processes contributing to the dielectric permittivity of these dimers. The low-frequency relaxation mode is attributed to an "end-over-end rotation" of the dipolar groups parallel to the director. The high-frequency relaxation mode is associated with precessional motions of the dipolar groups about the director. Various models are employed to describe the temperature-dependent behavior of the relaxation times for both modes. Particularly, the critical-like description via the dynamic scaling model seems to give not only quite good numerical fittings, but also provides a consistent physical picture of the orientational dynamics in accordance with findings from infrared (IR) spectroscopy. Here, as the longitudinal correlations of dipoles intensify, the m1 mode experiences a sudden upsurge in enthalpy, while the m2 mode undergoes continuous changes, displaying critical mode coupling behavior. Interestingly, both types of molecular motion exhibit a strong cooperative interplay within the lower temperature range of the NTB phase, evolving in tandem as the material's temperature approaches the glass transition point. Consequently, both molecular motions converge to determine the glassy dynamics, characterized by a shared glass transition temperature, Tg.

Enantiotropic ferroelectric nematic phase in a single compound.

The ferroelectric nematic phase became the centre of interest of scientists because of its unique physical properties. The uniqueness of this particular phase results in its monotropic character in all known NF materials. Here we present the very first example of a compound with an enantiotropic ferroelectric nematic phase. Compound 3JK is complementary with already well known NF materials, i.e. RM734 and DIO and is characterized by moderately high dielectric anisotropy.

Dielectric Study of Liquid Crystal Dimers: Probing the Orientational Order and Molecular Interactions in Nematic and Twist-Bend Nematic Phases.

Dielectric spectroscopy in frequencies that range from 10 Hz to 1 GHz has been used to study the molecular orientational dynamics of the two types of dimers that form the twist-bend nematic phase over a wide range of temperatures for both nematic and twist-bend nematic phases. The symmetrical and asymmetrical liquid crystal dimers with the cyanobiphenyl mesogenic groups were investigated. The results were analyzed within the framework of the molecular theory of dielectric permittivity for nematogens. The two molecular processes can be assigned to the reorientation of the monomeric unit: the high frequency one to the precessional rotation of the longitudinal components of the cyanobiphenyl groups (CN) and the second (low frequency) to the end-over-end rotation of the CN dipole around the short molecular axis. The precession mode, which is determined by the local order and is almost unaffected by the phase transition from the nematic to the twist-bend phase, while the end-over-end rotation clearly slowed down at the transition, as it is affected by the growth of the intermolecular interactions. The latter corresponds well to the fact revealed by IR spectroscopy about the longitudinal correlation of the molecular dipoles.

How Do Intermolecular Interactions Evolve at the Nematic to Twist-Bent Phase Transition?

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.

Study of the Experimental and Simulated Vibrational Spectra Together with Conformational Analysis of Thioether Cyanobiphenyl-Based Liquid Crystal Dimers.

Infrared spectroscopy (IR) and quantum chemistry calculations that are based on the density functional theory (DFT) have been used to study the structure and molecular interactions of the nematic and twist-bend phases of thioether-linked dimers. Infrared absorbance measurements were conducted in a polarized beam for a homogeneously aligned sample in order to obtain more details about the orientation of the vibrational transition dipole moments. The distributions to investigate the structure and conformation of the molecule dihedral angle were calculated. The calculated spectrum was compared with the experimental infrared spectra and as a result, detailed vibrational assignments are reported.

Structure of the twist-bend nematic phase with respect to the orientational molecular order of the thioether-linked dimers.

An analysis of the IR absorbance for the segmented functional groups of liquid crystal dimers mesogen and linker enabled the orientation order to be determined and information about the dipole interactions in the nematic and twist-bend nematic phases to be obtained. The long axis orientational order increases as the temperature decreases in the nematic phase, although much more slowly than for the classical nematics, and then reverses this trend in the twist-bend nematic phase due to the tilt of the molecules. In the nematic phase, the short axis of the molecule performs an isotropic uniform rotation and has a uniaxial alignment. In the twist-bend nematic phase, however, biaxial ordering occurs and grows significantly in accordance with the helical deformation of the director. Changes in the mean absorbance in the twist-bend nematic phase were observed: a decrease for the longitudinal dipole at the nematic-twist-bend nematic phase transition, thus emphasizing the antiparallel axial interaction of the dipoles, while the absorbance of the transverse dipoles remains unchanged up to 340 K, and then the latter become parallelly correlated.

Molecular biaxiality determines the helical structure - infrared measurements of the molecular order in the nematic twist-bend phase of difluoro terphenyl dimer.

Fourier-transform infrared polarized spectroscopy was employed, to obtain the three components of the infrared absorbance for a series of bent-shaped dimers containing double fluorinated terphenyl core (DTC5Cn, n = 5, 7, 9, 11). The data were used to calculate both uniaxial and biaxial order parameters, for various molecular groups of dimers. The molecule bend was estimated based on the observed differences between the uniaxial order parameters for the terphenyl core and central hydrocarbon linker. The orientational order, distinctly reverses its monotonic trend of increase to decrease at the transition temperature, from the uniaxial nematic to the twist-bend nematic phase as result of the director tilt in latter/(twist-bend) phase. The molecular biaxiality, which is negligible in the nematic phase, starts increasing on entering the twist-bend nematic phase, following a sin-square relationships with the tilt angle. The local director curvature is found to be controlled by the molecular biaxiality parameter.

The role of intermolecular interactions in stabilizing the structure of the nematic twist-bend phase.

The understanding of the relationship between molecular structure and the formation of the nematic twist-bend phase is still at an early stage of development. This is mainly related to molecular geometry, while the correlation between the nematic twist-bend phase and the electronic structure is ambiguous. To explore the electronic effect on properties and stabilization of the nematic twist-bend phase we investigated 2',3'-difluoro-4,4''-dipentyl-p-terphenyl dimers (DTC5Cn). We used polarized fourier transform infrared spectroscopy, which can, at least in principle, provide information about the ordering in the twist-bend phase. All dimers show a significant drop in the average value of the transition dipole moment for parallel dipoles at the transition from the nematic to the twist-bend phase, and an increase for perpendicular dipoles, despite remaining unchanged for the monomer. Density functional theory calculations were used to determine the geometric and electronic properties of the hydrogen bonded complexes. We have provided experimental and theoretical evidence of stabilization of the nematic twist-bend phase by arrays of multiple hydrogen bonds (XF⋯HX, X-benzene ring).

Temperature-dependent infrared spectroscopy studies of a novel antiferroelectric liquid-crystalline thiobenzoate.

The temperature-dependent infrared spectroscopy studies of one novel antiferroelectric liquid crystal (AFLC), known under the MHPSBO10 acronym, have been undertaken. The FT-IR measurements have been performed for homeotropic and planar heterogeneous sample geometries. The main order parameters have been determined and followed with temperature. The presented study delivers complex insight into the evolution of the vibrational spectrum upon phase transitions, covering the whole mesophase range. The experimental studies have been supported by theoretical studies of MHPSBO10 in confined geometries.

Complex vibrational analysis of an antiferroelectric liquid crystal based on solid-state oriented quantum chemical calculations and experimental molecular spectroscopy.

The experimental and theoretical vibrational spectroscopic study of one of a novel antiferroelectric liquid crystals (AFLC), known under the MHPSBO10 acronym, have been undertaken. The interpretation of both FT-IR and FT-Raman spectra was focused mainly on the solid-state data. To analyze the experimental results along with the molecular properties, density functional theory (DFT) computations were performed using several modern theoretical approaches. The presented calculations were performed within the isolated molecule model, probing the performance of modern exchange-correlations functionals, as well as going beyond, i.e., within hybrid (ONIOM) and periodic boundary conditions (PBC) methodologies. A detailed band assignment was supported by the normal-mode analysis with SQM ab initio force field scaling. The results are supplemented by the noncovalent interactions analysis (NCI). The relatively noticeable spectral differences observed upon Crystal to AFLC phase transition have also been reported. For the most prominent vibrational modes, the geometries of the transition dipole moments along with the main components of vibrational polarizability were analyzed in terms of the molecular frame. One of the goals of the paper was to optimize the procedure of solid-state calculations to obtain the results comparable with the all electron calculations, performed routinely for isolated molecules, and to test their performance. The presented study delivers a complex insight into the vibrational spectrum with a noticeable improvement of the theoretical results obtained for significantly attracting mesogens using modern molecular modeling approaches. The presented modeling conditions are very promising for further description of similar large molecular crystals.

Origin of the liquid-liquid phase transition for trans-1,2-dichloroethylene observed by IR spectroscopy.

IR vibrational spectroscopy has been employed to study liquid-liquid phase transitions of trans-1,2-dichloroethylene (TDCE). The temperature dependence of the vibrational frequency, band absorbance, and band broadening has been analyzed in the temperature range of 293-237 K. All peaks show distinct increases in their absorbancies at the temperature of 246.7 K accompanied by a frequency shift and bandwidth changes. Weak H...Cl hydrogen bonding has been suggested as the explanation for the overall behavior in a wide temperature range, whereas the significant changes in the spectrum at 246.7 K are probably due to molecular ordering originating from electrostatic interactions. The transition is well described by the model of the cooperative formation of locally favored structures.

Ab initio study of phenyl benzoate: structure, conformational analysis, dipole moment, IR and Raman vibrational spectra.

The molecular structure (bond distances and angles), conformational properties, dipole moment and vibrational spectroscopic data (vibrational frequencies, IR and Raman intensities) of phenyl benzoate were calculated using Hartree-Fock (HF), density functional (DFT), and second order Møller-Plesset perturbation theory (MP2) with basis sets ranging from 6-31G* to 6-311++G**. The theoretical results are discussed mainly in terms of comparisons with available experimental data. For geometric data, good agreement between theory and experiment is obtained for the MP2, B3LYP and B3PW91 levels with basis sets including diffuse functions. The B3LYP/6-31+G* theory level estimates the shape of the experimental functions for phenyl torsion around the Ph-O and Ph-C bonds well, but reproduces the height of the rotational barriers poorly. The B3LYP/6-31+G* harmonic force constants were scaled by applying the scaled quantum mechanical force field (SQM) technique. The calculated vibrational spectra were interpreted and band assignments were reported. They are in excellent agreement with experimental IR and Raman spectra.

Raman spectroscopic study of glutaraldehyde-stabilized collagen and pericardium tissue.

For the first time, Raman spectroscopy has been employed to investigate formation of cross-links in collagen and porcine pericardium tissue upon glutaraldehyde (GA) treatment. GA treatment causes a very high fluorescence background, which overlaps Raman bands. It has been found that short fixation time, i.e. 2 h, reduces background radiation significantly, providing new possibilities for studying changes in molecular structure of collagen upon GA modification. The observed changes in position and intensity of Raman bands allowed us to recognize different types of GA-collagen interactions. Strong spectral evidence has been found for the peptide contribution to the formation of the GA-collagen cross-links and for the formation of secondary amines via Schiff base intermediates, and pyridinium-type cross-links. The results also revealed that different hydration levels and a more complex structure of intact tissue in comparison to collagen preparation strongly influence the formation of a GA cross-linking network, e.g. ether-type bond is preferred to form in a less hydrated collagen preparation. Our results have shown that GA treatment causes an increase in water content of pericardium tissue and collagen.