Rod-like Compounds Research Articles

Supertwisted Chiral Gyroid Mesophase in Chiral Rod-Like Compounds.

Among the intriguing bicontinuous self-assembled structures, the gyroid cubic is the most ubiquitous. It is found in block and star polymers, surfactants with or without solvent, in thermotropic liquid crystals with end- or side-chains, and in biosystems providing structural color and modelling cell mitosis. It contains two interpenetrating networks of opposite chirality and is thus achiral if, as usual, the content of the two nets is the same. However, we now find that this is not the case for strongly chiral compounds. While achiral molecules follow the opposite twists of nets 1 and 2, molecules with a chiral center in their rod-like core fail to follow the 70° twist between junctions in net 2 and instead wind against it by -110° to still match the junction orientation. The metastable chiral gyroid is a high-entropy high-heat-capacity mesophase. The homochirality of its nets makes the CD signal of the thienofluorenone compounds close to that in the stable I23 phase with 3 isochiral nets.

The Influence of the Molecular Structure of Compounds on Their Properties and the Occurrence of Chiral Smectic Phases.

We have designed new chiral smectic mesogens with the -CH2O group near the chiral center. We synthesized two unique rod-like compounds. We determined the mesomorphic properties of these mesogens and confirmed the phase identification using dielectric spectroscopy. Depending on the length of the oligomethylene spacer (i.e., the number of methylene groups) in the achiral part of the molecules, the studied materials show different phase sequences. Moreover, the temperature ranges of the observed smectic phases are different. It can be seen that as the length of the alkyl chain increases, the liquid crystalline material shows more mesophases. Additionally, its clearing (isotropization) temperature increases. The studied compounds are compared with the structurally similar smectogens previously synthesized. The helical pitch measurements were performed using the selective reflection method. These materials can be useful and effective as chiral components and dopants in smectic mixtures targeted for optoelectronics and photonics.

Enantiomers Self-Sort into Separate Counter-Twisted Ribbons of the Fddd Liquid Crystal─Antiferrochirality and Parachirality.

The recently discovered orthorhombic liquid crystal (LC) phase of symmetry Fddd is proving to be widespread. In this work, a chiral hydroxybutyrate linkage is inserted into the molecular core of hexacatenar rodlike compounds, containing a thienylfluorenone fluorophore. In addition to more usual tools, the methods used include grazing-incidence X-ray scattering, modulated differential scanning calorimetry (DSC), flash DSC with rates up to 6000 K/s, and chiro-optical spectroscopies using Mueller matrix method, plus conformational mapping. Although pure R and S enantiomers form only a strongly chiral hexagonal columnar LC phase (Colh*), the racemic mixture forms a highly ordered Fddd phase with 4 right- and 4 left-handed twisted ribbon-like columns traversing its large unit cell. In that structure, the two enantiomers locally deracemize and self-sort into the columns of their preferred chirality. The twisted ribbons in Fddd, with a 7.54 nm pitch, consist of stacked rafts, each containing ∼2 side-by-side molecules, the successive rafts rotated by 17°. In contrast, an analogous achiral compound forms only the columnar phase. The multiple methods used gave a comprehensive picture and helped in-depth understanding not only of the Fddd phase but also of the "parachiral" Colh* in pure enantiomers with irregular helicity, whose chirality is compared to the magnetization of a paramagnet in a field. Unusual short-range ordering effects are also described. An explanation of these phenomena is proposed based on conformational analysis. Surprisingly, the isotropic-columnar transition is extremely fast, completing within ∼20 ms. A clear effect of phase on UV-vis absorption and emission is observed.

Planar and Vertical Alignment of Rod-like and Bent-core Liquid Crystals Using Functionalized Indium Tin Oxide Substrates

ABSTRACT Indium tin oxide (ITO) substrates are chemically modified with bent-shaped molecules and influence of these surface immobilised molecules on the alignment of bulk liquid crystal (LC) samples has been investigated. Bent-core (BC) compounds containing a dimethylchlorosilane moiety at the end of a terminal alkyl chain and a lateral alkyl chain are successfully attached to transparent conducting ITO substrates in an end-on (ITO-BC-t) and side-on (ITO-BC-l) oriented fashion to create stable permanent self-assembled BC layers on the substrates. Surface functionalization is thoroughly characterised and aligning ability of these BC-modified ITO substrates for orientation of bulk LC sample is evaluated for nematic phase of both rod-like and BCLC samples. The BC-modified substrates are effective in aligning the rod-like compounds in vertical (ITO-BC-t), planar orientations (ITO-BC-l) and the BC compounds in homeotropic (ITO-BC-t) alignment.

Long Rod-Like Liquid Crystal Containing Azobenzene and the Applications in Phase-Transition Regulation and Orientation of Nematic Liquid Crystal

Phase-transition and orientation of liquid crystal (LC) are two crucial factors for LC application. In this work, a long rod-like LC compound containing double azobenzene (M1) is successfully designed and synthesized. The combing technologies of nuclear magnetic resonance (1H NMR, 13C NMR) and Fourier transform infrared spectroscopy (FTIR) are used to identify the chemical structure of the molecule. Additionally, the polarized optical microscopy (POM), differential scanning calorimetry (DSC), and one-dimensional wide-angle X-ray diffraction (1D WAXD) experimental results show that M1 exhibits an ultrawide range of LC phases and a stable LC structure even at ultrahigh temperature, which indicates that this LC can be applied in some especial devices. Further, the compound M1 is used to tune the LC temperature range of the commercial LC 4-cyano-4′-pentylbiphenyl (5CB). A series of samples 1–7 are obtained through doping different contents of M1, which show different LC temperature ranges that are dependent on the composition ratio of M1 and 5CB. More interestingly, all resultant samples show spontaneous vertical orientation on the hydrophilic glass substrate. Meanwhile, due to the effect of azobenzene in the compound M1, a reversible transition between homeotropic to random orientation of the LC molecules is achieved when these LC cells are alternately exposed to UV irradiation and visible light, which implies that this material shows potential application in especial display and optical storage technologies.

Chiral Photoresponsive Liquid Crystalline Materials Derived from Cyanoazobenzene Central Core: Effect of UV Light Illumination on Mesomorphic Behavior

One of the most frequently utilized liquid crystalline (LC) materials is a rod-like (calamitic) compound 4-cyano-4′-pentylbiphenyl (5-CB). The main objective of this work is to enhance its functionality by introducing a photoresponsive diazenyl spacer in the aromatic core and replace the non-chiral pentyl chain with various chiral alkyl carboxylate units. The mesomorphic properties of the prepared materials have been studied using polarizing optical microscopy and differential scanning calorimetry. It has been found that materials with an extended aromatic system possess the liquid crystalline behavior. The studied LC materials have shown mesophases at lower temperatures than previously reported analogous substances. Furthermore, one of them exhibits a chiral orthogonal frustrated twist grain boundary smectic phase, which has not been previously observed for this structural type of materials. We also investigated photoresponse of the mesophases under illumination with UV-light (365 nm) using a polarizing optical microscope. A non-conventional photoresponse of the prepared materials in a crystalline phase is presented and discussed.

Chiral polymorphism in new imine based rod-like liquid crystals

New imine based rod-like compounds, composed of three-benzene-ring molecular core linked with azomethine as well as ester groups and terminated with (S)-3,7-dimethyloctyloxy chiral unit at one side have been synthesized. The other terminal position has been varied by using n-octyloxy/decyloxy/dodecyloxy groups to reveal chain length effect on mesophase behavior. The liquid crystalline properties of the new compounds have been investigated by polarizing optical microscopy, differential scanning calorimetry and electro-optic studies. The novel chiral calamitics derived from Schiff base or salicylaldimine-core show a chiral polymorphism comprising of blue phase and chiral nematic as well as smectics such as chiral tilted smectic and unidentified smectic mesophase.

Synthesis and mesomorphic properties of four ring, rod-like fluorene derivatives – the influence of the lateral substitution on mesomorphic properties of 2,7-bis(4-alkylphenyl)-fluorenes

ABSTRACTThis work presents new rod-like compounds being fluorene derivatives linked with other parts of the core at 2 and 7 positions – its synthesis and properties. The fluorene moiety is located in the central position of the four rings molecular core. The chain system in most cases was symmetrical and limited to pentyl or hexyl chains. To study the influence of the lateral substituents on mesomorphic properties two types of substituents have been incorporated, centrally located various short alkyl groups at fluorene’s 9,9 positions and outer core fluorosubstitutions located at side phenyl rings. All synthesised compounds exhibit liquid crystalline properties, where for laterally non-substituted and fluorosubstituted derivatives the dominant phases are smectics, while the nematics phases (nematic and chiral nematic – observed mostly on cooling cycle) occurs for compounds having alkyl substituents at 9,9 positions of fluorene. The synthetic methodology and mesomorphic properties of title compounds will be presented in detail as well as photophysical properties such as UV-visible absorption spectra and fluorescence spectra.

Chiral Octahydro-Binaphthol Compound-Based Thermally Activated Delayed Fluorescence Materials for Circularly Polarized Electroluminescence with Superior EQE of 32.6% and Extremely Low Efficiency Roll-Off.

Circularly polarized organic light-emitting diodes (CP-OLEDs) are particularly favorable for the direct generation of CP light, and they demonstrate a promising application in 3D display. However, up to now, such CP devices have suffered from low brightness, insufficient efficiency, and serious efficiency roll-off. In this study, a pair of octahydro-binaphthol (OBN)-based chiral emitting enantiomers, (R/S)-OBN-Cz, are developed by ingeniously merging a chiral source and a luminophore skeleton. These chirality-acceptor-donor (C-A-D)-type and rod-like compounds concurrently generate thermally activated delayed fluorescence with a small ΔEST of 0.037 eV, as well as a high photoluminescence quantum yield of 92% and intense circularly polarized photoluminescence with dissymmetry factors (|gPL |) of ≈2.0 × 10-3 in thin films. The CP-OLEDs based on (R/S)-OBN-Cz enantiomers not only display obvious circularly polarized electroluminescence signals with a |gEL | of ≈2.0 × 10-3 , but also exhibit superior efficiencies with maximum external quantum efficiency (EQEmax ) up to 32.6% and extremely low efficiency roll-off with an EQE of 30.6% at 5000 cd m-2 , which are the best performances among the reported CP devices to date.

Dual stimuli-responsive nano-structure transition of three-arm branched amphiphilic polymers containing ferrocene (Fc) and azobenzene (Azo) moieties in aqueous solution.

Amphiphilic polymers can self-assemble into various nanostructures in solution, which can find applications in many fields such as nanotechnology, drug delivery, and template synthesis. Herein, we report the controlled self-assembly and dual stimuli-responsive nanostructure transition of a class of three-arm branched amphiphilic polymers (AzoFcPEO) containing ferrocene (Fc) and azobenzene (Azo) moieties in aqueous solution. These amphiphilic polymers were synthesized by an esterification reaction of a variety of polyethylene oxide methyl ethers (Me-PEO) with 3-(6-ferrocenyhexyloxyl)-5-(6-azobenzenehexyloxy) benzoic acid. Both the isomerization of Azo and redox of Fc moieties can respectively change the amphiphilicity of these polymers to different degrees. Consequently, these amphiphilic polymers in aqueous solution can self-assemble into various nanostructures, such as spherical micelle, worm-like micelle, spherical compound micelle, rod-like compound micelle and vesicle dependent on the PEO molecular weight, applied stimuli, and polymer concentration. This work can offer tremendous possibilities not only for the fundamental science of the controlled self-assembly but also for establishing a suitable method for regulating the nanostructures of amphiphilic polymers in aqueous solution.

Electron Transfer around a Molecular Corner.

The distance dependence of electron transfer (ET) is commonly investigated in linear rigid rod-like compounds, but studies of molecular wires with integrated corners imposing 90° angles are very rare. By using spirobifluorene as a key bridging element and by substituting it at different positions, two isomeric series of donor-bridge-acceptor compounds with either nearly linear or angled geometries were obtained. Photoinduced ET in both series is dominated by rapid through-bond hole hopping across oligofluorene bridges over distances of up to 70 Å. Despite considerable conformational flexibility, direct through-space and through-solvent ET is negligible even in the angled series. The independence of the ET rate constant on the total number of fluorene units in the angled series is attributed to a rate-limiting tunneling step through the spirobifluorene corner. This finding is relevant for multidimensional ET systems and grids in which individual molecular wires are interlinked at 90° angles.

Diboron compound-based organic light-emitting diodes with high efficiency and reduced efficiency roll-off

Organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) materials are promising for the realization of highly efficient light emitters. However, such devices have so far suffered from efficiency roll-off at high luminance. Here, we report the design and synthesis of two diboron-based molecules, CzDBA and tBuCzDBA, which show excellent TADF properties and yield efficient OLEDs with very low efficiency roll-off. These donor–acceptor–donor (D–A–D) type and rod-like compounds concurrently generate TADF with a photoluminescence quantum yield of ~100% and an 84% horizontal dipole ratio in the thin film. A green OLED based on CzDBA exhibits a high external quantum efficiency of 37.8 ± 0.6%, a current efficiency of 139.6 ± 2.8 cd A−1 and a power efficiency of 121.6 ± 3.1 lm W−1 with an efficiency roll-off of only 0.3% at 1,000 cd m−2. The device has a peak emission wavelength of 528 nm and colour coordinates of the Commission International de l´Eclairage (CIE) of (0.31, 0.61), making it attractive for colour-display applications.

Elimination-Fusion Self-Assembly of a Nanometer-Scale 72-Nucleus Silver Cluster Caging a Pair of [EuW10 O36 ]9- Polyoxometalates.

The largest known polyoxometalate (POM)-templated silver-alkynyl cluster, [(EuW10 O36 )2 @Ag72 (tBuC≡C)48 Cl2 ⋅4 BF4 ] (SD/Ag20), was isolated under solvothermal conditions and structurally characterized. It was confirmed by single-crystal X-ray diffraction (SCXRD) as a {EuW10 }2 -in-{Ag72 } clusters-in-cluster rod-like compound. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) shows that such a double anion-templated cluster is assembled from a crucial single anion-templated Ag42 intermediate in the solution. The crystallization of Ag42 species (SD/Ag21), followed by SCXRD, gave an important clue about the assembly route of SD/Ag20 in solution: the Ag42 cluster eliminates six silver atoms laterally, then fuses together at the vacant face to form the final Ag72 cluster (elimination-fusion mechanism). The characteristic emission of [EuW10 O36 ]9- is well maintained in SD/Ag20. This work not only provides a new method for the synthesis of larger silver clusters as well as the functional integration of the silver cluster and POMs, but also gives deep insights about the high-nuclear silver cluster assembly mechanism.

Isothermal Chirality Switching in Liquid-Crystalline Azobenzene Compounds with Non-Polarized Light.

Spontaneous mirror-symmetry breaking is a fundamental process for development of chirality in natural and in artificial self-assembled systems. A series of triple chain azobenzene based rod-like compounds is investigated that show mirror-symmetry breaking in an isotropic liquid occurring adjacent to a lamellar LC phase. The transition between the lamellar phase and the symmetry-broken liquid is affected by trans-cis photoisomerization, which allows a fast and reversible photoinduced switching between chiral and achiral states with non-polarized light.

Prediction of cathodic E1/21 and E1/22 values for viologen-containing conjugated unimers and dimers from calculated pKb values of the aromatic substituents

A library of 18 conjugated, rod-like compounds with either one or two viologen residues were synthesized and characterized electrochemically. Containing up to 8 aromatic/heterocyclic rings in conjugation, the members of the library differ in the substitution pattern of electron-withdrawing or -donating groups on the aromatic substituents of the viologen units. The first and second half-wave potentials of each member were found to be linearly correlated with the calculated pKb values of the aromatic end-groups. This relationship will enable the half-wave potentials of related, novel, substituted viologen species to be predicted using a simple, empirical formula.

Second-harmonic generation and the influence of flexoelectricity in the nematic phases of bent-core oxadiazoles

ABSTRACTSecond-harmonic generation (SHG) in the nematic phase of bent-core oxadiazole-based liquid crystals (LCs) was studied and compared to that for the rod-like compound 4-cyano-4ʹ-n-octylbiphenyl (8CB). Weak, isotropically scattered second-harmonic (SH) light was observed for all materials, consistent with SHG by nematic director fluctuations. The SH intensity produced by the bent-core materials was found to be up to ~ 3.4 times that of 8CB. We discuss this result in terms of the dependence of SH intensity on temperature, elastic constants and flexoelectric coefficients. We have calculated the latter by using a molecular field approach with atomistic modelling, thus demonstrating how molecular parameters contribute to the flexoelectric coefficients and illustrating the potential of this method for predicting the flexoelectric behaviour of bent-core LCs. We show that the increased SH signal in the bent-core compounds is partly due to their nematic phases being at a much higher temperature, and also potentially due to them having greater flexoelectric coefficients, up to ~1.5 times those of 8CB. These estimates are consistent with reports of increased flexoelectric coefficients in bent-core compounds in comparison to rod-like compounds.

Photomodulated Supramolecular Chirality in Achiral Photoresponsive Rodlike Compounds Nanosegregated from the Helical Nanofilaments of Achiral Bent-Core Molecules.

We prepared a nonchiral mixture of achiral bent-core molecules and photoresponsive rodlike liquid crystalline (LC) molecules. With the help of the isothermal photochemical nematic (N)-isotropic (Iso) phase transition of the photoresponsive rodlike LC molecules, the corresponding phase transition from a dark conglomerate BX phase to another distinguishable dark conglomerate B4 phase took place in the mixture. A large circular dichroism (CD) signal originating from supramolecular chirality was detected in the initial BX phase. On the other hand, the detected CD signal was decreased in the B4 phase after UV irradiation. Interestingly, the decreased CD signal could be reverted to the initial CD signal with visible irradiation. This chiroptical process revealed in this work was stable and reversible and thus opens up the possibility of practical applications such as rewritable optical storage.

Polar structure of disclination loops in nematic liquid crystals probed by second-harmonic-light scattering.

Angle-resolved, second-harmonic-light scattering (SHLS) measurements are reported for three different classes of thermotropic nematic liquid crystals (NLCs): polar and nonpolar rodlike compounds and a bent-core compound. Results revealing well-defined scattering peaks are interpreted in terms of the electric polarization induced by distortions of the nematic orientational field ("flexopolarity") associated with inversion wall defects, nonsingular disclinations, analogous to Neel walls in ferromagnets, that often exhibit a closed loop morphology in NLCs. Analysis of the SHLS patterns based on this model provides a "proof-of-concept" for a potentially useful method to probe the flexopolar properties of NLCs.

Achiral straight-rod liquid crystals indicating local biaxiality and ferroelectric switching behavior in the smectic A and nematic phases

Local biaxiality was realized through perfluoroarene–arene and CH/F interactions in the smectic A and nematic phases of rod-like compound 1a, and ferroelectric switching was observed.

Diindolo[2,3-b:2',3'-f]pyrrolo[3,2-b]pyrroles as electron-rich, ladder-type fluorophores: synthesis and optical properties.

Previously unknown ladder-type heteroacenes were synthesized in just two steps from aromatic amines, 2-nitrobenzaldehydes, and biacetyl. A recently discovered multicomponent process affording 1,4-dihydropyrrolo[3,2-b]pyrroles was followed by the Cadogan reaction, which resulted in simultaneous closure of two additional pyrrole rings. Rod-like compounds synthesized in this way were stable in the absence of light, and they were transformed into bis(tert-butoxycarbonyl) derivatives. The rigid herringbone-like structure resulted in a strong absorption in the λ=350-410 nm region and very strong violet and blue emission, which was bathochromically shifted relative to the emission of the parent 1,4-dihydropyrrolo[3,2-b]pyrroles. The optical properties of these compounds strongly suggest that the conjugation spanned the entire π system. The HOMO energy level was located at -4.6 to -5.1 eV.