New columnar liquid crystal materials based on luminescent 2-methoxy-3-cyanopyridines

A new series of donor-acceptor-donor (D-A-D) type luminescent mesogens carrying 2-methoxy-3-cyanopyridine as a central core linked with variable alkoxy chain lengths (m = 6 and 8) as terminal substituents was synthesized and characterized using spectral methods. The newly synthesized molecules were subjected to single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), differential scanning calorimetric (DSC), polarizing optical microscopy (POM), and fluorescence emission studies in order to ascertain their mesogenic and photophysical properties. The SCXRD data on 4a and 4b reveal that the presence of short intermolecular contacts, viz. C-H center dot center dot center dot N, C-H center dot center dot center dot O, C-H center dot center dot center dot pi, and pi center dot center dot center dot pi interactions, is responsible for their crystal packing. The measured torsion angle values indicate that molecules possess distorted non-planar structure. The DSC, POM, and PXRD studies confirm that all the molecules show thermotropic liquid crystalline behaviour and exhibit rectangular columnar phase. Further, their UV-visible and fluorescence spectral studies reveal that the target molecules are luminescent displaying a strong absorption band in the range of 335-340 nm and a blue fluorescence emission band in the range of 395-425 nm (both in solution and film state) with good fluorescence quantum yields (10-49 %).

Herringbone to cofacial solid state packing via H-bonding in diketopyrrolopyrrole (DPP) based molecular crystals: influence on charge transport

Themono-alkylation of DPP derivatives leads to cofacial pi-pi stacking via H-bonding unlike their di-alkylated counterparts, which exhibit a classical herringbone packing pattern. Single crystal organic field-effect transistor (OFET) measurements reveal a significant enhancement of charge carrier mobility for mono-hexyl DPP derivatives.

Assignment of the C-13 NMR spectrum by correlation to dipolar coupled proton-pairs and estimation of order parameters of a thiophene based liquid crystal

Materials with widely varying molecular topologies and exhibiting liquid crystalline properties have attracted considerable attention in recent years. C-13 NMR spectroscopy is a convenient method for studying such novel systems. In this approach the assignment of the spectrum is the first step which is a non-trivial problem. Towards this end, we propose here a method that enables the carbon skeleton of the different sub-units of the molecule to be traced unambiguously. The proposed method uses a heteronuclear correlation experiment to detect pairs of nearby carbons with attached protons in the liquid crystalline core through correlation of the carbon chemical shifts to the double-quantum coherences of protons generated through the dipolar coupling between them. Supplemented by experiments that identify non-protonated carbons, the method leads to a complete assignment of the spectrum. We initially apply this method for assigning the C-13 spectrum of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl oriented in the magnetic field. We then utilize the method to assign the aromatic carbon signals of a thiophene based liquid crystal thereby enabling the local order-parameters of the molecule to be estimated and the mutual orientation of the different sub-units to be obtained.

Studies on the phase behavior of lyotropic liquid crystal in DAD/C4OH/n-C8H18/D2O system

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD)/n-butanol (C4OH)/octane (n-C8H18)/deuteron (D2O) system were studied to determine the phase regions and were investigated by H-2-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods. The results indicate that the lamellar, hexagonal and cubic liquid crystals all exist in the above system. Keeping the weight ratio of DAD and C4OH constant,the microphase structure, H-2 quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

Phase transitions from the solid state of monatomic elements

The principle aims of this thesis include the development of models of sublimation and melting from first principles and the application of these models to the rare gases.

A simple physical model is constructed to represent the sublimation of monatomic elements. According to this model, the solid and gas phases are two states of a single physical system. The nature of the phase transition is clearly revealed, and the relations between the vapor pressure, the latent heat, and the transition temperature are derived. The resulting theory is applied to argon, krypton, and xenon, and good agreement with experiment is found.

For the melting transition, the solid is represented by an anharmonic model and the liquid is described by the Percus-Yevick approximation. The behavior of the liquid at high densities is studied on the isotherms kT/∈ = 1.3, 1.8, and 2.0, where k is Boltzmann's constant, T is the temperature, and e is the well depth of the Lennard-Jones 12-6 pair potential. No solutions of the PercusYevick equation were found for ρσ³ above 1.3, where ρ is the particle density and σ is the radial parameter of the Lennard-Jones potential. The liquid structure is found to be very different from the solid structure near the melting line. The liquid pressures are about 50 percent low for experimental melting densities of argon. This discrepancy gives rise to melting pressures up to twice the experimental values.

Two Glass Transitions Associated to Different Dynamic Disorders in the Nematic Glassy State of a Non-Symmetric Liquid Crystal Dimer Dopped with gamma-Alumina Nanoparticles

In the present work, the nematic glassy state of the non-symmetric LC dimer -(4-cyanobiphenyl-4-yloxy)--(1-pyrenimine-benzylidene-4-oxy) undecane is studied by means of calorimetric and dielectric measurements. The most striking result of the work is the presence of two different glass transition temperatures: one due to the freezing of the flip-flop motions of the bulkier unit of the dimer and the other, at a lower temperature, related to the freezing of the flip-flop and precessional motions of the cyanobiphenyl unit. This result shows the fact that glass transition is the consequence of the freezing of one or more coupled dynamic disorders and not of the disordered phase itself. In order to avoid crystallization when the bulk sample is cooled down, the LC dimer has been confined via the dispersion of -alumina nanoparticles, in several concentrations.

Lowering the excitation threshold of a random laser using the dynamic scattering states of an organosiloxane smectic A liquid crystal

Smectic A liquid crystals, based upon molecular structures that consist of combined siloxane and mesogenic moieties, exhibit strong multiple scattering of light with and without the presence of an electric field. This paper demonstrates that when one adds a laser dye to these compounds it is possible to observe random laser emission under optical excitation, and that the output can be varied depending upon the scattering state that is induced by the electric field. Results are presented to show that the excitation threshold of a dynamic scattering state, consisting of chaotic motion due to electro-hydrodynamic instabilities, exhibits lower lasing excitation thresholds than the scattering states that exist in the absence of an applied electric field. However, the lowest threshold is observed for a dynamic scattering state that does not have the largest scattering strength but which occurs when there is optimization of the combined light absorption and scattering properties. © 2012 American Institute of Physics.

UV durable colour pigment doped SmA liquid crystal composites for outdoor trans-reflective bi-stable displays

High brightness trans-reflective bi-stable displays based on smectic A (SmA) liquid crystals (LCs) can have nearly perfect transparency in the clear state and very high reflection in the scattered state. Because the LC material in use is stable under UV radiation, this kind of displays can stand for strong day-light and therefore be ideal for outdoor applications from e-books to public signage and advertisement. However, the colour application has been limited because the traditional colourants in use are conventional dyes which are lack of UV stability and that their colours are easily photo bleached. Here we present a colour SmA display demonstrator using pigments as colourant. Mixing pigments with SmA LCs and maintain the desirable optical switching performance is not straightforward. We show here how it can be done, including how to obtain fine sized pigment nano-particles, the effects of particle size and size distribution on the display performance. Our optimized pigments/SmA compositions can be driven by a low frequency waveform (∼101Hz) to a scattered state to exhibit colour while by a high frequency waveform (∼103Hz) to a cleared state showing no colour. Finally, we will present its excellent UV life-time (at least >7.2 years) in comparison with that of dye composition (∼2.4 years). The complex interaction of pigment nano-particles with LC molecules and the resulting effects on the LC electro-optical performances are still to be fully understood. We hope this work will not only demonstrate a new and practical approach for outdoor reflective colour displays but also provide a new material system for fundamental liquid crystal colloid research work. © 2012 SPIE.

Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking

By using the solid-state MAS NMR technique, the hydrothermal stabilities (under 100% steam at 1073 K) of HZSM-5 zeolites modified by lanthanum and phosphorus have been studied. They are excellent zeolite catalysts for residual oil selective catalytic cracking (RSCC) processes. It was indicated that the introduction of phosphorus to the zeolite via impregnation with orthophosphoric acid led to dealumination as well as formation of different Al species, which were well distinguished by Al-27 3Q MAS NMR. Meanwhile, the hydrothermal stabilities of the zeolites (P/HZSM-5, La-P/HZSM-5) were enhanced even after the samples were treated under severe conditions for a prolonged time. It was found that the Si-O-Al bonds were broken under hydrothermal conditions, while at the same time the phosphorous compounds would occupy the silicon sites to form (SiO)(x)Al(OP)(4 - x) species. With increasing time, more silicon sites around the tetrahedral coordinated Al in the lattice can be replaced till the aluminum is completely expelled from the framework. The existence of lanthanum can partially restrict the breaking of the Si-O-Al bonds and the replacement of the silicon sites by phosphorus, thus preventing dealumination under hydrothermal conditions. This was also proved by P-31 MAS NMR spectra. (C) 2004 Elsevier Inc. All rights reserved.

Solid-state dye-sensitized solar cells using TiO2 nanotube arrays on FTO glass

Highly ordered, vertically oriented TiO2 nanotube arrays were prepared by potentiostatic anodization of titanium on FTO-coated glass substrate and for the first time successfully applied in the fabrication of solid-state dye sensitized solar cells (SSDSCs), giving a power conversion efficiency of 1.67% measured under an irradiation of air mass 1.5 global (AM 1.5 G) full sunlight. Furthermore, 3.8% efficiency was reached with a 2.8 mu m thin TiO2 nanotube array film based on a metal free organic dye using ionic liquid electrolyte.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

SOLID-STATE C-13 NMR-STUDIES ON THE CONDENSATION AND SULFONATION OF FURFURYL ALCOHOL AND TRIS (2-HYDROXYETHYL) ISOCYANURATE

The condensation and sulfonation of furfuryl alcohol (FA) and FA with tris (2-hydroxyethyl) isocyanurate (THEIC) and the crosslinking product structures were studied by means of solid-state C-13 NMR. The reaction of formalin with FA linear oligomer terminated by 2-methyl furan took place in the presence of the phase transfer catalyst (C4H9)4N+I-. The reaction of the terminated oligomer with a large amount of sulfuric acid as well as the former reaction was examined. The effects of some main reaction conditions on the crosslinking condensation and sulfonation were also discussed.