Correlation of Kauzman temperature with odd-even effect in n-alkanes

A unique correlation has been established between Kauzmann temperature (Tk1) and the odd–even effect in n‐alkanes. The derived new parameter, i.e., Tm/Tk1 obtained from entropy conservation at Tk1, when plotted against chain length, provides a much sharper odd–even contrast than entropy of fusion plot reported earlier. © 1996 American Institute of Physics.

Odd-even effect in the elastic modulii of alpha,omega-Alkanedicarboxylic acids

Nanoindentation studies on alpha,omega-alkanedicarboxylic acids reveal that the elastic modulus, E, shows an odd-even alternation in exactly the same manner as the melting temperature, T-m. The results are consistent with the hypothesis that the strained molecular conformations in the odd diacids are the reasons for these alternations in T-m. The same packing features that lower T-m in the odd acids lead to easy accommodation of the deformation during nanoindentation and hence their low E.

Flexoelectric and elastic coefficients of odd and even homologous bimesogens.

It is known that bimesogenic liquid crystals exhibit a marked "odd-even" effect in the flexoelastic ratio (the effective flexoelectric coefficient to the average elastic coefficient), with the ratio being higher for the "odd-spaced" bimesogens (those with an odd number of alkyl groups in the spacer chain) than their neighboring even-spaced counterparts. To determine the contribution of each property to the flexoelastic ratio, we present experimental results on the flexoelectric and elastic coefficients of two homologous nonsymmetric bimesogens which possess odd and even alkyl spacers. Our results show that, although there are differences in the flexoelectric coefficients, there are substantially larger differences in the effective elastic coefficient. Specifically, the odd bimesogen is found to have both a low splay elastic coefficient and a very low bend elastic coefficient which, when combined, results in a significantly lower effective elastic coefficient and consequently a higher flexoelastic ratio.

Flexoelectric and elastic coefficients of odd and even homologous bimesogens.

It is known that bimesogenic liquid crystals exhibit a marked "odd-even" effect in the flexoelastic ratio (the effective flexoelectric coefficient to the average elastic coefficient), with the ratio being higher for the "odd-spaced" bimesogens (those with an odd number of alkyl groups in the spacer chain) than their neighboring even-spaced counterparts. To determine the contribution of each property to the flexoelastic ratio, we present experimental results on the flexoelectric and elastic coefficients of two homologous nonsymmetric bimesogens which possess odd and even alkyl spacers. Our results show that, although there are differences in the flexoelectric coefficients, there are substantially larger differences in the effective elastic coefficient. Specifically, the odd bimesogen is found to have both a low splay elastic coefficient and a very low bend elastic coefficient which, when combined, results in a significantly lower effective elastic coefficient and consequently a higher flexoelastic ratio.

Odd-even oscillations of SHG efficiencies in twin NLO chromophores

Twin NLO chromophores having two azobenzene units linked by a flexible polymethylene spacer of varying lengths are shown to exhibit odd-even oscillations in their second harmonic generation (SHG) efficiencies, when measured in the powder form. These twin systems were designed to also exhibit liquid cystallinity, and indeed most of them do exhibit a nematic mesophase. The anticipated odd-even oscillations, in both their isotropization transition temperatures (Ti) and isotropization entropies (Delta Si), were also observed. The odd-even oscillation of the SHG efficiencies has been ascribed to a more effective cancellation of mesogenic dipoles in the even twins as compared to their odd counterparts, due to a preferred centrosymmetric packing in the former case. Based on the behaviour of these twin chromophoric molecules, it may be anticipated that such odd-even oscillations will also be observed in the analogous main chain NLO polymers.

Succinate esters: odd-even effects in melting points

Dialkyl succinates show a pattern of alternating behavior in their melting points, as the number of C atoms in the alkane side chain increases, unlike in the dialkyl oxalates Joseph et al. (2011). Acta Cryst. B67, 525-534]. Dialkyl succinates with odd numbers of C atoms in the alkyl side chain show higher melting points than the immediately adjacent analogues with even numbers. The crystal structures and their molecular packing have been analyzed for a series of dialkyl succinates with 1 - 4 C atoms in the alkyl side chain. The energy difference (Delta E) between the optimized and observed molecular conformations, density, Kitaigorodskii packing index (KPI) and C-H center dot center dot center dot O interactions are considered to rationalize this behavior. In contrast to the dialkyl oxalates where a larger number of moderately strong C-H center dot center dot center dot O interactions were characteristic of oxalates with elevated melting points, here the molecular packing and the density play a major role in raising the melting point. On moving from oxalate to succinate esters the introduction of the C2 spacer adds two activated H atoms to the asymmetric unit, resulting in the formation of stronger C-H center dot center dot center dot O hydrogen bonds in all succinates. As a result the crystallinity of long-chain alkyl substituted esters improves enormously in the presence of hydrogen bonds from activated donors.

Crystal engineering in two dimensions: An approach to molecular nanopatterning

We describe a surprising cooperative adsorption process observed by scanning tunneling microscopy (STM) at the liquid−solid interface. The process involves the association of a threefold hydrogen-bonding unit, trimesic acid (TMA), with straight-chain aliphatic alcohols of varying length (from C7 to C30), which coadsorb on highly oriented pyrolytic graphite (HOPG) to form linear patterns. In certain cases, the known TMA “flower pattern” can coexist temporarily with the linear TMA−alcohol patterns, but it eventually disappears. Time-lapsed STM imaging shows that the evolution of the flower pattern is a classical ripening phenomenon. The periodicity of the linear TMA−alcohol patterns can be modulated by choosing alcohols with appropriate chain lengths, and the precise structure of the patterns depends on the parity of the carbon count in the alkyl chain. Interactions that lead to this odd−even effect are analyzed in detail. The molecular components of the patterns are achiral, yet their association by hydrogen bonding leads to the formation of enantiomeric domains on the surface. The interrelation of these domains and the observation of superperiodic structures (moiré patterns) are rationalized by considering interactions with the underlying graphite surface and within the two-dimensional crystal of the adsorbed molecules. Comparison of the observed two-dimensional structures with the three-dimensional crystal structures of TMA−alcohol complexes determined by X-ray crystallography helps reveal the mechanism of molecular association in these two-component systems.

Structure-flexoelastic properties of bimesogenic liquid crystals

In this paper, we report on the flexoelastic and viscoelastic ratios for a number of bimesogens compounds with the same generic structure. Values are obtained indirectly by measuring the flexoelectro-optic response in the chiral nematic phase. By varying the molecular structure we alter the bend angle, transverse dipole moment, and length of the molecule. First, to examine the influence of the bend angle we use a homologous series whereby the only alteration in the molecular structure is the number of methylene units in the aliphatic spacer, n. Results show that the flexoelastic ratio, e K, and the effective flexoelectric coefficient, e, both exhibit an odd-even effect with values for n=odd being greater than that for n=even. This is understood in terms of an increase in the bend angle of the molecule and an increase in the transverse dipole moment. Second, in order to investigate the impact of the dipole moment, we have altered the mesogenic units so as to vary the longitudinal dipole moment and used different linkages in the aliphatic spacer in an attempt to alter the transverse dipole moment. Qualitatively, the results demonstrate that the odd-spaced bimesogen with larger transverse dipole moments exhibit larger flexoelastic ratios. © 2007 The American Physical Society.

Emission characteristics of a homologous series of bimesogenic liquid-crystal lasers.

In this study we have fabricated eight different liquid-crystal lasers using the same gain medium but different homologues from the bimesogenic series alpha-(2',4-difluorobiphenyl-4'-yloxy)-omega-(4-cyanobiphenyl-4'-yloxy)alkanes, whereby the number of methylene units in the spacer chain varied from n=5 to n=12. To quantify the performance of these lasers, the threshold energy and the slope efficiency were extracted from the input-output characteristics of each laser. A clear odd-even effect was observed when both the excitation threshold and the slope efficiency were plotted as a function of the number of methylene units in the spacer chain. In all cases, the bimesogen lasers for which n is even exhibit lower threshold energies and higher slope efficiencies than those for which n is odd. These results are then interpreted in terms of the macroscopic physical properties of the liquid-crystalline compounds. In accordance with a previous study [S. M. Morris, A. D. Ford, M. N. Pivnenko, O. Hadeler, and H. J. Coles, Phys. Rev. E. 74, 061709 (2006)], a combination of a large birefringence and high order parameters are found, in the most part, to correlate with low-threshold energy and high slope efficiency. This indicates that the threshold and slope efficiency are dominated by the host macroscopic properties as opposed to intermolecular interactions between the dye and the liquid crystal. However, certain differences in the slope efficiency could not be explained by the birefringence and order parameter values alone. Instead, we find that the slope efficiency is further increased by increasing the elastic constants of the liquid-crystal host so as to decrease the scattering losses incurred by local distortions in the director field under high-energy optical excitation.

Structure-flexoelastic properties of bimesogenic liquid crystals.

In this paper, we report on the flexoelastic and viscoelastic ratios for a number of bimesogens compounds with the same generic structure. Values are obtained indirectly by measuring the flexoelectro-optic response in the chiral nematic phase. By varying the molecular structure we alter the bend angle, transverse dipole moment, and length of the molecule. First, to examine the influence of the bend angle we use a homologous series whereby the only alteration in the molecular structure is the number of methylene units in the aliphatic spacer, n . Results show that the flexoelastic ratio, e/K , and the effective flexoelectric coefficient, e , both exhibit an odd-even effect with values for n=odd being greater than that for n=even . This is understood in terms of an increase in the bend angle of the molecule and an increase in the transverse dipole moment. Second, in order to investigate the impact of the dipole moment, we have altered the mesogenic units so as to vary the longitudinal dipole moment and used different linkages in the aliphatic spacer in an attempt to alter the transverse dipole moment. Qualitatively, the results demonstrate that the odd-spaced bimesogen with larger transverse dipole moments exhibit larger flexoelastic ratios.

Studies on liquid crystalline bis[4-(p-phenoxy)-phenylbenzoate] alkyldicarboxylate

A new series of liquid crystals of bis[4-(p-phenoxy)-phenylbenozoate] alkyldicarboxylate which contain two rigid groups connected by a flexible spacer was synthesized. These liquid crystals show nematic phase and were found to show odd-even effect in isotropization temperature and entropy change.

RAMAN-SPECTROSCOPIC STUDY OF LAYER STRUCTURE COMPOUND [N-CNH2N+1NH3]2ZNCL4

The C-H stretching, C-H bending, C-C stretching and the low-frequency vibration regions have been investigated by Raman spectroscopy for [n-CnH2n+1NH3]2 ZnCl4 with n=7 approximately 12, 16. It is found that their frequency and relative intensities are related to the length of carbon chain in the molecules and present the odd-even effect to carbon atom numbers in chain. Some changes in spectra are interpreted in terms of the different molecular packing and interaction of chain.

RAMAN-SPECTROSCOPIC STUDY OF THE PEROVSKITE LAYER STRUCTURE COMPOUNDS - [N-CNH2N+1NH3]2ZNCL4

The C-H stretching, C-H bending, C-C stretching and the low-frequency vibrational regions have been investigated by Raman spectroscopy for [n-CnH2n+1NH3]2ZnCl4 with n = 7-12, 16. The frequencies and relative intensities are related to the length of the carbon chain in the molecules and present the odd-even effect of the carbon atom numbers in the chains. Some changes in the spectra are interpreted in terms of the different molecular packing.