Nematic Liquid Crystal Solvent Research Articles

Probing the orientation of porphyrin oligomers in a liquid crystal solvent – a triplet state electron paramagnetic resonance study

ABSTRACTLinear porphyrin oligomers have found various applications as synthetic molecular wires in the context of light harvesting, solar energy conversion and molecular electronics. In many of these applications a partial ordering of the molecules helps to improve the reaction efficiency or device performance. In this work we study the orientational properties of the building blocks of such porphyrin-based molecular wires, namely a porphyrin monomer and the corresponding butadiyne-bridged dimer. The porphyrins have been embedded in the nematic liquid crystal solvent 4-cyano-4'-pentylbiphenyl (5CB) and the anisotropic properties of their photogenerated triplet states were characterised by transient electron paramagnetic resonance (EPR) spectroscopy. When aligned in strong magnetic fields, the liquid crystal molecules impose their orientational anisotropy onto the solute guest molecules whose orientation-dependent magnetic properties can then be explored. The line shape analysis of the porphyrin triplet state EPR spectra – highly sensitive to small conformational changes – confirms the orientation of the zero-field-splitting (ZFS) tensors previously determined for these molecules by magnetophotoselection experiments. A biaxial distribution function is shown to be necessary to simulate the experimental EPR data. The biaxial behaviour, in conjunction with symmetry considerations, allows an unambiguous assignment of the three ZFS tensor axes to the molecular axes. From the determined orientational distributions of the porphyrins in 5CB, the biaxial order parameters for both molecules were calculated.

NMR of orientationally ordered short-chain hydrocarbons

ABSTRACTThe proton NMR spectra of the straight-chain hydrocarbons from methane to -hexane orientationally ordered in nematic liquid-crystal solvents are reviewed. The theory behind reorientation-vibration coupling (that explains the anisotropic splittings observed in the spectrum of methane) is discussed. This coupling is also important for ethane where the torsional motion about the C–C bond becomes an issue. The ratios of propane to ethane dipolar couplings are found to be independent of liquid crystal and of temperature: this demonstrates that the hydrocarbons are ‘magic solutes’, i.e. their orientational order results from a single anisotropic interaction that involves short-range size-and-shape effects. The longer chains -butane, -pentane and -hexane (which give extremely complicated NMR spectra) exist in several symmetry-unrelated conformers. The spectra are analysed with the aid of evolution strategies. The dipolar couplings obtained are used in a model-free analysis (that is based on the constant ratio between ethane and propane dipolar couplings) to explore important information about the intermolecular potential. For example, the orientational order of longer conformers is favoured by the nematic phase.

The effect of concentration and molecular weight of polycarbonate on the elastic constants of a nematic liquid crystal solvent

We utilized the Light Scattering from Anisotropy of Turbidity (LSAT) method and determined the three Frank’s elastic constants of; "splay" (K1), "twist" (K2) and "bend" (K3), in dilute solutions of polycarbonate (PC) in 4-pentyl-4’-cyanobiphenyl (5CB) nematic liquid crystal solvent. Within the limited solubility range of PC/5CB solutions, we determined the elastic constants of 5CB as a function of the concentration and molecular weight of PC. The results showed that K2 increases, K1 and K3 decrease, whereas K1/K3 and <K> ratio remain almost invariant by increasing the PC concentration and molecular weight.In contrast to the theoretical models and experimental data, the values and trends of K1, K2 and K3 moduli indicate that, increase of K2 at the expense of K1 and K3 moduli is due to extended chain conformation PC polymer structure and enhancment of lateral interactions between PC and 5CB moieties.

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.

A model-free temperature-dependent conformational study of n-pentane in nematic liquid crystals.

The proton NMR spectra of n-pentane orientationally ordered in two nematic liquid-crystal solvents are studied over a wide temperature range and analysed using covariance matrix adaptation evolutionary strategy. Since alkanes possess small electrostatic moments, their anisotropic intermolecular interactions are dominated by short-range size-and-shape effects. As we assumed for n-butane, the anisotropic energy parameters of each n-pentane conformer are taken to be proportional to those of ethane and propane, independent of temperature. The observed temperature dependence of the n-pentane dipolar couplings allows a model-free separation between conformer degrees of order and conformer probabilities, which cannot be achieved at a single temperature. In this way for n-pentane 13 anisotropic energy parameters (two for trans trans, tt, five for trans gauche, tg, and three for each of gauche+ gauche+, pp, and gauche+ gauche-, pm), the isotropic trans-gauche energy difference Etg and its temperature coefficient Etg(') are obtained. The value obtained for the extra energy associated with the proximity of the two methyl groups in the gauche+ gauche- conformers (the pentane effect) is sensitive to minute details of other assumptions and is thus fixed in the calculations. Conformer populations are affected by the environment. In particular, anisotropic interactions increase the trans probability in the ordered phase.

Crystal Axis Control of Soluble Organic Semiconductors in Nematic Liquid Crystal Solvents Based on Electric Field

We investigated a control of the crystalline orientation of soluble organic semiconductor single crystals using liquid crystal solvents aligned by the electric field to improve the performance of organic thin-film transistors. We clarified that the semiconductor single crystal grows to the direction parallel to the liquid crystal alignment oriented by the lateral electric field.

Self-assembly of a liquid crystal ABA triblock copolymer in a nematic liquid crystal solvent

An ABA type triblock copolymer, consisting of liquid crystalline polymer (LCP, poly(4-cyanobiphenyl-4-oxyundecylacrylate)) ‘A’ end blocks and a deuterated polystyrene (dPS) ‘B’ mid block (LCP–dPS–LCP) was successfully synthesized by atom transfer radical polymerization (ATRP). The number average molecular weight (Mn) of LCP–dPS–LCP was LCP (7.1 K)–dPS (19.4 K)–LCP (7.1 K) with a polydispersity index (PDI) of 1.41. LCP–dPS–LCP was self-assembled in a nematic liquid crystal solvent of 4-pentyl-4′-cyanobiphenyl (5CB) into spherical micelles with a LCP corona and a dPS core, in which dPS was folded to produce a V-shape structure. Micellar structures of LCP–dPS–LCP in 5CB were examined by small angle neutron scattering at various block copolymer concentrations and temperatures using a curve fitting method. The critical micelle concentration was 0.25 wt% and the self-assembled micelles dissociated into unimers at 33 °C, which is lower than the nematic to isotropic transition temperature (Tni) of 5CB (36 °C). The entropic penalty imposed on dPS by the ordered nematic state of the 5CB solvent caused phase separation of the flexible dPS block to form micelles, which vanished above the Tni of the 5CB solvent. Magnetic field-induced global orientation of 5CB revealed the structure of the dPS core of the micelle to be prolate (an elongated sphere) oriented with its long axis along the direction of the applied magnetic field.

Vertically Aligned Carbon Film Synthesized from Magnetically Oriented Polyacetylene using Morphology Retaining Carbonization

Polyacetylene (PA) films with vertically aligned fibril morphology were synthesized in homeotropic nematic liquid crystal (N-LC) solvent by using a magnetic field of 5 Tesla as an external perturbation. Scanning electron microscope (SEM) photographs indicated that the lengths of fibrils from the substrate were 5−35 µm, depending on polymerization time. Carbonization was carried out using iodine-doped PA film and a morphology-retaining car - bonization method. From the SEM results, we confirmed that the vertical morphology of the PA remains unchanged even after carbonization at 800 o C. The weight loss of the films due to carbonization at 800 o C is about 20% of the weight of the film before iodine doping. It is ex - pected that vertically aligned carbon might be a precursor for preparing vertical graphite ma- terials, which materials could be useful for electrochemical energy storage and cell electrodes.

Self-Assembly of dPS-Liquid Crystalline Diblock Copolymer in a Nematic Liquid Crystal Solvent

A diblock copolymer dPS(9.1K)-b-LCP(7.2K), the number in parentheses represents the number-averaged molecular weight) with a deuterated polystyrene (dPS) block connected to a side group liquid crystal polymer [poly(6-(4′-cyanobiphenyloxy)hexyl acrylate, LCP] was self-assembled into ∼78 Å spherical micelles with a dPS core and LCP corona in a small-molecule nematic liquid crystal solvent, 4-pentyl-4′-cyanobiphenyl (5CB). The micellar structures were examined by small angle neutron scattering (SANS) at various block copolymer concentrations and temperatures. The SANS data was analyzed further using a curve fitting method. The critical micelle concentration (CMC) was as low as ∼0.0027 wt % and the self-assembled micelles were dissociated reversibly into a unimer state at 33 °C, which is lower than the nematic to isotropic transition temperature (Tni) of 5CB (36 °C). The entropic penalty imposed on the dPS by the ordered nematic state of the LC solvent caused phase separation of the flexible dPS block to form micelles and vanished above the Tni of the LC solvent. A low CMC of ∼0.0027 wt % suggests that 5CB was a strong selective solvent for dPS-b-LCP in the nematic state. The global orientation of 5CB, produced by a magnetic field (MF, 1.2 T) revealed the structure of the dPS core of the micelle to be prolate (elongated sphere) oriented with the long axis along the applied MF direction.

Alignment of Small Organic Solutes in a Nematic Solvent: The Effect of Electrostatic Interactions

The origin of the alignment with respect to the director observed for solutes in a nematic host remains unclear, and various mechanisms ranging from steric repulsions to dispersive or electrostatic interactions have been invoked. Here we present atomistic molecular dynamics (MD) computer simulations of rigid solutes of small dimensions dissolved in a nematic liquid crystal solvent, 4-n-pentyl-4'cyanobiphenyl (5CB), that aim to quantitatively predict the orientational order. We have validated the results comparing the dipolar couplings obtained by atomistic simulation with their experimental NMR counterparts. To help assess the separate effect of the various types of anisotropic interactions on the orientational order of solutes, we have modeled solute molecules with their partial atomic charges present or absent (switching them to zero), finding that, at least for the cases studied, the alignment mechanism is largely dominated by steric and van der Waals dispersive forces rather than Coulomb ones. We have compared the anisotropic aligning potential with the predictions of the Maier-Saupe and surface tensor models and discussed their performance.

Phase Behavior of Poly(n‐butyl acrylate) and Poly(2‐ethylhexyl acrylate) in Nematic Liquid Crystal E7

AbstractSummary: This paper reports on the phase behavior of photochemically crosslinked poly(n‐butyl acrylate) (PABu) and poly(2‐ethylhexyl acrylate) (PEHA) networks in a nematic liquid crystal (LC) solvent. The swelling properties of these networks were studied as a function of temperature using a low molecular weight LC (LMWLC), which is an eutectic mixture of cyanoparaphenylenes named E7. To obtain different polymer network densities, the ratio of the reactive monomers ABu (or EHA) to the crosslinking agent hexanedioldiacrylate (HDDA) was varied prior to polymerization/crosslinking reactions. Immersion of these networks in an excess of LC solvent allowed for the measurement of size increase by polarizing optical microscopy in terms of temperature. Diameter ratios were calculated considering swollen to dry network states of the samples. The uptake of LMWLC inside the network preferentially takes place around the nematic to isotropic transition temperature of the solvent. Phase diagrams in the concentration‐temperature framework were given and discussed as a function of crosslinking degree of the polymer network and temperature and phase behavior of the solvent.

Enhancement of the cholesteric induction power by macrocyclization in liquid crystal dimers with a chiral spacer

A liquid crystal dimer with a chiral spacer increases the helical twisting power in a nematic liquid crystal solvent by a factor of four because the two tails are connected. In the macrocyclized dimer, the two mesogens are fixed in a skewed overlapping alignment with the handedness determined by the spacer’s chirality.

3H NMR of the tritiated isotopologues of methane in nematic liquid-crystal solvents

The NMR spectra of the tritiated isotopologues of methane dissolved in several nematic liquid-crystalline solvents are measured. The spectral parameters obtained agree extremely well with those predicted from earlier NMR studies of the deuterated isotopologues, providing excellent confirmation of the theory for vibration–reorientation interaction developed earlier.

Entanglement-free fibrils of aligned polyacetylene films that produce single nanofibers

An aligned polyacetylene (PA) film was synthesized in a macroscopically-aligned nematic liquid crystal (N-LC) solvent using a gravity-flow method. Long and single nanofibers of less than 100 nm in radius were successfully prepared by ultrasonication of the aligned PA film immersed in ethanol. The usual PA film was synthesized in an isotropic solvent, such as toluene, only yielding short and non-dispersed fibers after the ultrasonication due to the entangled fibril morphology. Entanglement-free fibrils of the aligned PA were well-separated into single fibrils through ultrasonication, even without a surfactant.

Uniaxially ordered conjugated polymer film prepared by electrochemical polymerization in a nematic liquid crystal with rubbing orientation method showing redox-driven tunable dichroism

We demonstrate electrochemical polymerization of an aromatic conjugated monomer in a macroscopically aligned nematic liquid crystal. This method is a combination of employment of liquid crystal as the electrolyte solution, a rubbing technique, and electropolymerization. The resulting polymer film shows linear dichroism and anisotropy. Polarizing optical microscopy reveals that the polymer film is uniformly ordered on a macroscopic scale. These results indicate that the conjugated main chains grow along a director of the aligned nematic liquid crystal solvent.

Solute order parameters in liquid crystals from NMR spectra solved with evolutionary algorithms: Application of double Maier–Saupe Kobayashi–McMillan theory

We obtain dipolar couplings via a novel application of evolutionary algorithms solving for multiple spin-systems simultaneously and automatically from the NMR spectra of several solutes in several nematic and smectic liquid crystal solvents. The order parameters obtained from the dipolar couplings are used to test a novel Hamiltonian that includes two Maier–Saupe nematic terms plus Kobayashi–McMillan smectic A terms. It is shown that this Hamiltonian can rationalize the NMR experiments with physically reasonable smectic order parameters and Hamiltonian prefactors.

Orientational order of near D3h solutes in nematic liquid crystals

Solutes that are similar in size, have a shape that is close to D(3h) symmetry but contain dissimilar substituent groups (methyl versus chloro, contributing different electrostatic interactions to the anisotropic intermolecular potential), are used to delineate the short- and long-range anisotropic intermolecular interactions that lead to solute orientational order in nematic liquid crystals. The short-range interactions should be similar for all solutes and for D(3h) symmetry should yield a single independent order parameter, whereas the long-range interactions are expected to differ with solute. Short-range size and shape mechanisms account for solute orientational order measured in magic mixtures (e.g., 55 wt % ZLI-1132/N-p-ethoxybenzylidene-p(')-n-butylaniline), whereas additional mechanisms are required in other nematic liquid-crystal solvents. The results obtained for long-range interactions cannot be rationalized in detail using simple mean-field models that incorporate solute dipoles, quadrupoles, or polarizabilities. The results suggest that details of the solute electrostatics may need to be incorporated into the description of the anisotropic intermolecular potential.

Mechanisms of solute orientational order in nematic liquid crystals

The order parameters of a number of different solutes dissolved in a number of different nematic liquid-crystal solvents are measured and compared. It is shown that the order parameters can all be rationalized with the ansatz that there exist two independent ordering mechanisms operating in the liquid crystals employed. With this ansatz it is possible to fit the experimental order parameters to better than 5%. This opens the possibility of the accurate prediction of order parameters in ordered liquids.

Lattice Boltzmann algorithm to simulate isotropic-nematic emulsions

We present lattice Boltzmann simulations of the dynamical equations of motion of a drop of isotropic fluid in a nematic liquid crystal solvent, both in the absence and in the presence of an electric field. The coupled equations we solve are the Beris-Edward equations for the dynamics of the tensor order parameter describing the nematic solvent, the Cahn-Hilliard equation for the concentration evolution, and the Navier-Stokes equations for the determination of the instantaneous velocity field. We implement the lattice Boltzmann algorithm to ensure that spurious velocities are close to zero in equilibrium. We first study the effects of the liquid crystal elastic constant, K, anchoring strength, W, and surface tension, sigma, on the shape of the droplet and on the director field texture in equilibrium. We then consider how the drop behaves as the director field is switched by an applied electric field. We also show that the algorithm allows us to follow the motion of a drop of isotropic fluid placed in a liquid crystal cell with a tilted director field at the boundaries.

Anisotropic Diffusion of Elongated and Aligned Polymer Chains In a Nematic Solvent

The translational diffusion constant, D, of a polymer solute in a single-domain, nematic liquid crystal solvent (5CB) is measured in directions parallel and perpendicular to the nematic director using a fluorescence two-beam, cross-correlation technique. The solute under investigation is the stiff, conjugated polymer, MEH-PPV. The ratio D parallel/D perpendicular) of diffusion constants (parallel and perpendicular to the director) is observed to be 1.9 +/- 0.3. This is surprisingly small considering that MEH-PPV is known to be both elongated and highly aligned along the liquid crystal director of 5CB. We therefore argue that the structural order parameter of the solvent governs the anisotropy of the diffusion of the solute.