Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction.

Morphology influences the functionality of covalent organic networks and determines potential applications. Here, we report for the first time the use of Zincke reaction to fabricate, under either solvothermal or microwave conditions, a viologen-linked covalent organic network in the form of hollow particles or nanosheets. The synthesized materials are stable in acidic, neutral, and basic aqueous solutions. Under basic conditions, the neutral network assumes radical cationic character without decomposing or changing structure. Solvent polarity and heating method determine product morphology. Depending upon solvent polarity, the resulting polymeric network forms either uniform self-templated hollow spheres (HS) or hollow tubes (HT). The spheres develop via an inside-out Ostwald ripening mechanism. Interestingly, microwave conditions and certain solvent polarities result in the formation of a robust covalent organic gel framework (COGF) that is organized in nanosheets stacked several layers thick. In the gel phase, the nanosheets are crystalline and form honeycomb lattices. The use of the Zincke reaction has previously been limited to the synthesis of small viologen molecules and conjugated viologen oligomers. Its application here expands the repertoire of tools for the fabrication of covalent organic networks (which are usually prepared by dynamic covalent chemistry) and for the synthesis of viologen-based materials. All three materials-HT, HS, and COGF-serve as efficient adsorbents of iodine due to the presence of the cationic viologen linker and, in the cases of HT and HS, permanent porosity.

Influence of chirality on the thermal and electric properties of the columnar mesophase exhibited by homomeric dipeptides.

We present the first investigation of the influence of chirality on the thermal and electric properties in a biologically important homomeric dipeptide that exhibits a hexagonal columnar liquid crystal mesophase. The peptide employed has two chiral centres, and thus the two possible enantiopures are the (R,R) and (S,S) forms having opposite chirality. The measurements reported the span of the binary phase space between these two enantiopures. Any point in the binary diagram is identified by the enantiomeric excess Xee (the excess content of the R,R enantiopure over its S,S counterpart). We observe that the magnitude of Xee plays a pivotal role in governing the properties as evidenced by X-ray diffraction (XRD), electric polarization (Ps), dielectric relaxation spectroscopy (DRS) measurements, and the isotropic-columnar transition temperature. For example, XRD shows that while other features pointing to a hexagonal columnar phase remain the same, additional short-range ordering, indicating correlated discs within the column, is present for the enantiopures (Xee = ±1) but not for the racemate (Xee = 0). Similarly, an electric-field driven switching whose profile suggests the phase structure to be antiferroelectric is seen over the entire binary space, but the magnitude is dependent on Xee; interestingly the polarization direction is axial, i.e., along the column axis. DRS studies display two dielectric modes over a limited temperature range and one mode (mode 2) connected with the antiferroelectric nature of the columnar structure covering the entire mesophase. The relaxation frequency and the thermal behaviour of mode 2 are strongly influenced by Xee. The most attractive effect of chirality is its influence on the polar order, a measure of which is the magnitude of the axial polarization. This result can be taken to be a direct evidence of the manifestation of molecular recognition and the delicate interplay between chiral perturbations and the magnitude of the polar order, a feature attractive from the viewpoint of devices based on, e.g., remnant polarization-a currently hot topic. To add further dimension to the work, the DRS measurements are also extended to elevated pressures.

Self-assembly of luminescent N-annulated perylene tetraesters into fluid columnar phases.

A new class of N-annulated perylene tetraesters and their N-alkylated derivatives has been synthesized. N-Annulated perylene tetraesters stabilize a hexagonal columnar phase over a broad temperature range. The hexagonal columnar phase exhibited by these compounds shows good homeotropic alignment with few defects. Annulation in the bay region of the perylene tetraesters enhanced the width of the mesophase compared with the parent tetraesters. N-Alkylation of these compounds perturbed the self-assembly behaviour and the resulting compounds were non-mesomorphic. A bright green luminescence was visible under long wavelength UV light. These properties suggest that these materials may have promising applications in organic electronics.

IR regulation through preferential placement of h-BN nanosheets in a polymer network liquid crystal.

Recently, there has been a great deal of interest in devices which effectively shield near-infrared light with an additional feature of external field tunability, particularly for energy-saving applications. This article demonstrates an approach for fabricating a highly efficient near-infrared regulating device based on a polymer network liquid crystal reinforced with nanosheets of hexagonal-boron nitride (BN). The device achieves ∼84% IR scattering capability over a wavelength range of 800-2300 nm, and can also be regulated by an electric field. Interestingly, the observed high IR regulation is despite individual components of the composite being IR transparent, in stark contrast to earlier attempted incorporation of IR-absorbing/scattering particles. Detailed experimental characterization methods including FESEM corroborated with EDS and Raman spectroscopy suggest that the preferential positioning of the BN nanosheets, a consequence of the photo-polymerization process, is responsible for the observed feature. The IR reflectivity/back scattering that is doubled upon incorporation of the nanosheets results in an enhanced convective/radiative heat barrier capability, as evidenced by thermal imaging and significant (2 °C) reduction in ambient temperature upon one-Sun illumination. Numerical simulation results are also found to be in good agreement with the observed enhanced reflectance values for the BN-incorporated case. The presence of BN augments the mechanical rigidity of the system by a factor of 6.8 without compromising on the device operating voltage. The protocol employed is quite general and thus advantageous with far-reaching applications in passive cooling of buildings and structures, in thermal camouflaging, and in overall energy management.

Ambipolar Columnar Self-assembled Organic Semiconductors based on Heteroatom bay-Annulated Perylene Bisimides.

Highly electron-deficient heteroatom (N, S, Se) bay-annulated PBIs exhibiting ordered columnar phase over a wide mesomorphic range including ambient temperature are reported in this manuscript. These compounds with six peripheral n-decyloxy chains exhibited absorption spectra with high molar extinction coefficients, electron-deficient nature and self-assembling behaviour. A detailed comparison with the PBIs bearing six peripheral n-decyl chains was also carried out to get the valuable insights on the structure-property relations in this important class of organic semiconductors. Both of the PBI series were tested for their charge carrier mobility by space charge limited current method and found that they exhibit ambipolar conductivity. This is in contrary to the vast body of literature, where most of the PBI based semiconductors exhibit electron transport behaviour. In general, PBIs derived from tri-n-alkyl anilines exhibit higher mobility values than the PBIs derived from tri-n-alkoxy anilines. Especially, the ambipolar S-annulated PBI derived from tri-n-alkyl aniline exhibited highest hole (8.39×10-3  cm2 /V.s) and electron (1.5×10-2  cm2 /V.s) mobility values and promising for the application in organic electronics.

Twist-bend nematic drops as colloidal particles: Electric instabilities.

The mesogen 1,''7''-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB), doped with a small quantity of an amphiphilic compound, is examined in its biphasic state in which twist-bend nematic (N_{TB}) drops are dispersed in the isotropic fluid. Various flexoelectric and electrokinetic responses of small drops in their escaped-radial-like (ER) geometry, and also of larger ones with parabolic focal conic defects, are discussed. A pair of confocal parabolas with their axes along the applied low-frequency electric field undergo periodic dimensional changes so as to contribute flexoelectrically to free-energy reduction. In an ER droplet, the same result is achieved by periodic relocations of the hedgehog core. Sine-wave fields of low frequency and high voltage excite patterned states near zero-voltage crossings and homeotropic alignment at peak voltages. ER drops also exhibit electrohydrodynamic effects; in relatively weak fields, they undergo translatory motion with a velocity that is a quadratic in the field strength; the drift, which occurs over a very wide frequency range, extending from dc to MHz region, is enabled by radial symmetry breaking that their off-centered geometry entails; and the drift direction reverses across a critical frequency. In high fields, vortical flows occurring within an ER N_{TB} drop become discernible. The hydrodynamic effects are discussed based on the Taylor-Melcher leaky dielectric model.

Dimer-parity-dependent odd-even effects in photoinduced transitions to cholesteric and twist grain boundary smectic-C

We describe investigations on the influence of the flexible spacer parity and length of the guest photoactive liquid-crystalline dimers in guest-host mixtures exhibiting photoinduced transitions involving isotropic (I), cholesteric (N^{*}), and twist grain boundary smectic-C^{*} (TGBC^{*}) phases. Despite a small concentration (3 wt. %) of the guest molecules, the transition temperatures and their photodriven shift (δT) show a strong odd-even parity (of the dimer) dependent effect, with the even-parity systems having a larger value than their odd-parity counterparts; δT is larger for the N^{*}-TGBC^{*} transition than for the I-N^{*} one. The photocalorimetric measurements corroborate these features in addition to showing that, in comparison with the absence-of-ultraviolet (UV) case, the transition enthalpy (ΔH) of the I-N^{*} transition in the UV-on case is diminished by 33 and 12% for the mixtures with even- and odd-parity dimers, respectively. The duration for relaxation from the isothermal photodriven transition also exhibits general features of an odd-even influence. Molecular dynamics simulations demonstrate the presence of significant conformational heterogeneity and associated shift in the conformational space on photostimulation of the guest molecules. The change in the effective shape and nematic order parameter is more pronounced in the even-parity system.

Structure, stability, and electro-optic features of nematic drops in 1

Binary mixtures of the mesogen [1″,7″-bis(4-cyanobiphenyl-4'-yl)heptane] and a long chain amphiphile (e.g., 2-octadecoxypropanol) are examined for the structure, stability, and electro-optical behavior of nematic drops dispersed in the isotropic phase, in planar cells. Subjected to tangential boundary conditions, the drops adopt, besides the escaped concentric and untwisted bipolar geometries, the less common bound vortex geometry with a pair of half-strength disclination lines. The concentric drop, as it grows, switches its axis from an in-layer to the layer-normal direction corresponding to the stablest of all geometries. Bipolar drops in equilibrium have their axes parallel to the easy axis of the cell. Obliquely oriented bipolar drops rotate to attain the equilibrium disposition by the shorter of the clockwise and anticlockwise routes, the extent of rotation decreasing exponentially with time. The bipolar structure is marginally less stable than the concentric, and transforms to the latter geometry occasionally. In bound vortex drops, the separation between the lines varies as the drop diameter, the bipolar and concentric geometries appearing as the limiting cases. The complex course of Fréedericksz transition in all the different types of drops terminates in the division of the original large drop into many smaller drops, each with a surface charge 2, in conformity with the Poincaré-Hopf theorem. In low frequency electric fields, concentric drops exhibit flexoelectro-optic rotation in evidence of their escaped character.

Electric response of topological dipoles in nematic colloids with twist-bend nematic droplets as the dispersed phase.

Colloidal systems comprising solid or fluid particles dispersed in nematic monodomains are known to be a convenient means to study topological defects. Recent experiments have shown that twist-bend nematic (N_{TB}) droplets in a nematic matrix act as colloidal particles that lead to the formation of elastic dipoles, quadrupoles, and their ordered clusters. In this study, we examine the effect of low-frequency (f∼mHz) electric fields on such defect configurations. We find that (i) the hyperbolic hedgehogs of elastic dipoles shift toward the negative electrode in static fields and perform oscillatory motion in AC fields, indicating the presence of nonvanishing flexoelectric polarization in the field-free state; (ii) the elastic dipoles, propelled by forces of backflow due to coupled flexoelectric and dielectric distortions, drift uniformly along their axes with the N_{TB} drops in lead; (iii) the translational velocity v_{d} increases linearly with both f and the diameter of N_{TB} drops; and (iv) with increasing applied voltage U, v_{d}(U) exhibits a monotonic, slightly nonlinear variation at f≤200mHz, tending toward linearity at higher frequencies.

Transparent Triboelectric Nanogenerator Based on Thermoplastic Polyurethane Films.

This study aims at investigating flexible and transparent thermoplastic polyurethane (TPU) as a novel material for triboelectric nanogenerator (TENG) devices with a polyethylene terephthalate layer. Devices having TPU-either as a flat film or as electrospun micrometer-dimension fibers with varying concentrations of TPU-were tested. The best output performing device provided 21.4 V and 23 µA as open-circuit voltage and short-circuit current respectively, with the application of a small force of 0.33 N indicating the high efficiency of the device. Devices with flat films-obtained using the doctor-blade (DB) technique-have high transparency (80%) as well as high TENG output. The topography of the TPU layer, characterized by atomic force microscopy, reveals nanoscale roughness of the film surface. Finally, we demonstrate that gentle hand tapping on the TENG device can power upto 11 light-emitting diodes (LEDs). The high transparency, lightweight, simple fabrication, flexibility, and robust features of such device make it an added value for various optoelectronic applications.

Confinement-driven weakening of the rotator phase transitions in an alkane through a possible tricritical point.

We report calorimetric and X-ray measurements in the R1, R2, and R5 rotator phases of a long chain alkane (n-tetracosane) in bulk and confined to porous matrices (PTFE and Anopore) of two different length scales. Probing the order within and normal to the layers, in the Anopore case having a mesoscopic length scale (200 nm), drastic weakening of the R2-R1 and R1-R5 transitions is seen. The effect on the latter is to such an extent that it results in the first observation of a confinement-driven second order transition in these systems. A significant reduction of the temperature range of the R1 phase is also seen in the Anopore case, a feature argued to cause the change in the order of the transition. Comparisons are also made on the recent prediction of such a point in a Landau model. These findings, while paving a new means of realizing a tricritical point, will lead to better understanding of finite size effects in alkanes.

Saddle-splay-induced periodic edge undulations in smectic-A disks immersed in a nematic medium.

We report experimental studies on the phase behavior of binary mixtures of 1″,7″-bis(4-cyanobiphenyl-4'-yl)heptane (CB7CB) and 4,4-diheptyloxyazoxybenzene, which exhibit, apart from the nematic (N) and twist-bend nematic (N_{TB}) phases, the induced smectic-A (Sm-A) phase for weight fraction of CB7CB between 0.05 and 0.70. In planar nematic layers, the N_{TB} phase separates as droplets of tactoidlike planform; the chirality of droplets manifests in the optical dissimilarity between their opposite angular ends. Our main result is that, in the appropriate two phase region, Sm-A nuclei with positive dielectric anisotropy change over to disks immersed in the nematic above some electric field, their edges decorated by periodic bright spots, a result which was earlier reported in another binary system exhibiting the induced Sm-A phase [R. Pratibha and N. V. Madhusudana, Physica A 224, 9 (1996)10.1016/0378-4371(95)00311-8]. We develop a simple theory for the threshold of this distortion, which is a periodic undulation of the edge of the disk, demonstrating that it arises from saddle-splay elasticity of Sm-A, the low Sm-A-N interfacial tension unable to suppress the distortion. The observed increases in the number of bright spots with field, and with the radius of the disk at a given field, in both the experimental systems are also accounted for by the model. The distortion, which results in the most direct visualization of saddle splay in Sm-A, is also exhibited by disks nucleating on surfaces treated for homeotropic anchoring.

Pretransitional behaviour in the vicinity of the isotropic-nematic transition of strongly polar compounds.

The isotropic-nematic transition, being weakly first order, exhibits pretransitional effects signifying the appearance of the nematic-like regions in the isotropic phase. In the isotropic phase, strongly polar liquid crystals, such as the popular alkyl and alkoxy cyano biphenyl behave in a non-standard fashion: whereas far away from the transition the dielectric constant ε(iso) has a 1/T dependence (a feature also commonly seen in polar liquids), on approaching the nematic phase the trend reverses resulting in a maximum in ε(iso), at a temperature slightly above the transition, an effect explained on the basis of short-range correlations with an antiparallel association of the neighbouring molecules. Recently, there has been a revival in studies on this behaviour to possibly associate it with the order of transition. Here we report dielectric measurements carried in the vicinity of this transition for a number of compounds having different molecular structures including a bent core system, but with a common feature that the molecules possess a strong terminal polar group, nitro in one case and cyano in the rest. Surprisingly, the convex shape of the thermal variation of ε(iso) was more an exception than the rule. In materials that exhibit such an anomaly we find a linear correlation between δε = (ε(peak)-ε(IN))/ε(IN) and δT = T(peak)-T(IN), where ε(peak) is the maximum value of the dielectric constant in the isotropic phase, ε(IN) the value at the transition, and T(peak) and T(IN) the corresponding temperatures.

Nanophase Segregation of Nanostructures: Induction of Smectic A and Re-Entrance in a Carbon Nanotube/Nematic Liquid Crystal Composite.

Although representing drastically different chemical natures and types of interactions, the similarity of shape anisotropy of the constituents has created much interest in composites of calamitic liquid crystals (LCs) and carbon nanotubes (CNTs). Despite significant volume of studies on the physical properties of such composites, influence of CNTs on the celebrated re-entrant phenomenon in LCs has not been studied. We report here that a small concentration of CNTs doped to a "nematic mesophase-only" material not only induces the layered smectic A mesophase but also leads to the nematic-smectic-nematic re-entrant sequence as well, demonstrating the delicate interplay between the two entities. To explain this unusual observation, we propose nanophase segregation of the CNT as a possible mechanism. A combination of Flory-Huggins theory and Landau-de Gennes theory has also been provided supporting the observed feature.

Transforming a C 3-Symmetrical Liquid Crystal to a π-Gelator by Alkoxy Chain Variation.

Rational understanding of the structural features involving different noncovalent interactions is necessary to design a liquid crystal (LC) or an organogelator. Herein, we report the effect of the number and positions of alkoxy chains on the self-assembly induced physical properties of a few π-conjugated molecules. For this purpose, we designed and synthesized three C 3-symmetrical molecules based on oligo(p-phenylenevinylene), C 3 OPV1-3. The self-assembly properties of these molecules are studied in the solid and solution states. All of the three molecules follow the isodesmic self-assembly pathway. Upon cooling from isotropic melt, C 3 OPV1 having nine alkoxy chains (-OC12H25) formed a columnar phase with two-dimensional rectangular lattice and retained the LC phase even at room temperature. Interestingly, when one of the -OC12H25 groups from each of the end benzene rings is knocked out, the resultant molecule, C 3 OPV2 lost the LC property, however, transformed as a gelator in toluene and n-decane. Surprisingly, when the -OC12H25 group from the middle position is removed, the resultant molecule C 3 OPV3 failed to form either the LC or the gel phases.

Effect of Pressure on Dielectric and Frank Elastic Constants of a Material Exhibiting the Twist Bend Nematic Phase.

We report the first investigation on the effect of applied pressure on the now well-known dimer α,ω bis(4,4'-cyanobiphenyl)heptane (CB7CB) that exhibits two types of nematic: the regular uniaxial nematic (N) and the recently discovered twist-bend nematic (NTB) phase. At atmospheric pressure, the thermal behavior of ε⊥, the permittivity normal to the director in the N phase decreases on entering the NTB wherein the value represents permittivity orthogonal to the helical axis. Application of pressure initially decreases the magnitude of the change in ε⊥ and with further increase in pressure exhibits an increase in the value. Such a change in the feature of ε⊥ is similar to that obtained at room pressure when the monomeric heptyloxy cyanobiphenyl (7OCB) is doped to CB7CB at a high concentration of 50%. The dielectric anisotropy exhibits a trend reversal with temperature, the extent of which is affected at high pressures. Another salient feature of the study is the effect that pressure has on the Frank bend elastic constant K33. Over the pressure range studied K33 enhances by a large factor of 5. In contrast, the splay elastic constant exhibits a much smaller change of only 70%. The pressure-temperature phase boundary has a much smaller slope for the N-NTB transformation than for the isotropic-N transition. We propose that all these features can be understood in terms of the relative population of the more energetic horseshoe and lower energy extended conformer adopted by the CB7CB molecule. The extended conformer is favored at lower temperatures or at higher pressures. This argument is validated by X-ray diffraction experiments at atmospheric pressure on the binary mixture of CB7CB and 7OCB, mentioned above.

Light-induced changes of optical and electrical properties in bent-core azo compounds.

We have studied the optical and electrical properties of two bent-core substances with an azo linkage in their cores. Pump-probe laser studies, direct textural observations, and spectrophotometric recordings show an initial decrease of light transmission, which at larger light intensities (approximately 1 mW/mm2) is followed by a bleaching. Simultaneously the electrical properties (electric conductivity, antiferroelectric polarization, switching threshold, and switching time) decreased monotonically with increasing light intensities. The monotonic decrease of electrical properties indicates that the darkening and bleaching have the same origin, namely, the photochemical isomerization of the azo linkage from the trans to the cis isomer. The material with cis isomer has a lower clearing point and phase separates from the trans-rich domains. Initially the size of the separated isotropic domains is below the visible range, which causes increased scattering. As the size of the isotropic domains increase the scattering disappears and the transmittance becomes the average of the transmittances in the polar tilted smectic and isotropic phases.

Effect of pressure on the photoinduced nematic-isotropic phase transition.

We report the results of high-pressure studies on the photoinduced nematic-isotropic phase transition. It is observed that pressure has a significant influence on the shift in the transition temperature caused by uv radiation. We propose a possible mechanism to explain the observed results.

Anomalous intensity dependence of optical reorientation in azo-dye-doped nematic liquid crystals.

The intensity dependence of optical nonlinearity in a nematic liquid crystal doped with an azo-dye is investigated. The reorientational part of the nonlinearity changes from self-defocusing to self-focusing character while the intensity passes through the saturation value of trans-cis photoisomerization. This observation, in accordance with previous models, indicates that the optical torque generated by the trans-isomers is of opposite sign than the torque generated by the cis-isomers. At very low intensities a further reorientational nonlinearity was found, which is attributed to light-induced orientational redistribution of adsorbed molecules at the surface.

X-ray and dielectric measurements of the smectic- A -hexatic- B transitionin bulk and confined geometries.

We report x-ray and dielectric measurements on a liquid crystal exhibiting a smectic- A -hexatic- B (Sm- A -Hex- B ) transition in bulk and confined geometries. The confined geometry experiments have been performed by filling the compound, n -butyl 4(') - n -hexyloxybiphenyl-4-carboxylate, into Anopore membranes with 20 nm pore size. The surprising result seen in the x-ray studies on both the bulk and the Anopore samples is the presence of unusually strong second harmonic reflection arising from the smectic layers in both the Sm- A and Hex- B phases. In fact, the third harmonic reflection is also observed in the entire temperature range of the Hex- B phase and close to the transition in the Sm- A phase of the bulk sample, with the ratio of I(2qo) / I(qo), and I(3qo) / I(qo) being approximately 1/40 and 1/470, respectively (here I(qo), I(2qo), and I(3qo) correspond to the peak intensities of the first, second, and third harmonic reflections). These features point to the fact that the layering is much better defined in this system, unlike the usual description of pure sinusoidal mass density wave with a typical value of 10(-4) for I(2qo) / I(qo). Another notable feature observed is that whereas the extent of positional correlations of the molecules within the smectic layer, is comparable in the Sm- A phase of the bulk and Anopore samples, the correlations are reduced in the Hex- B phase. In the bulk as well as the Anopore case, the critical behavior of the positional correlations is found to be well described by a power-law expression with the exponent alpha being slightly larger for the Anopore sample. It is also seen that the weak first order nature of the transition seen in the bulk, gets weakened further, perhaps becoming second order. Despite such significant differences between the bulk and Anopore samples, the dynamics associated with the director fluctuations is only slightly influenced by confinement.