Liquid Crystal Complexes Research Articles

Thermal and optical studies on induced smectic phases of inter molecular hydrogen bonded liquid crystals between decyloxy benzoic acid and citric acid

ABSTRACTHydrogen bonded liquid crystal complex (HBLC) is prepared from mesogenic 4-decyloxy benzoic acid (10OBA) and aliphatic nonmesogenic citric acid (CA). Liquid crystal (LC) phases are investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) studies. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (NMR) validate the intermolecular complementary, cyclic type of hydrogen bond (HB) and molecular environment in the designed HBLC complex. Mesomorphic phases like nematic, smectic X (Sm X) and smectic G (Sm G) are characterized by various textures and using different techniques such as POM, DSC and optical tilt angle measurements. Thermal span width and thermal stability factor for the observed phase is calculated. The complexes are prepared in different mole ratio and their corresponding influences on the phase transitions are discussed. Also it is observed that the HB units play a vital role in stabilizing the new Sm X phase. The variation in thermal stability of smectic phases due to the influence of aromatic cores and length of end chain in the different mole ratio of the present HBLC complexes are also discussed. The variation of tilt angle with respect to temperature in the smectic phase has been experimentally calculated and analyzed. The lowered melting and clearing transition temperatures and extended thermal span width in the Sm X phase are also reported.

Design, Synthesis and Characterization of Hydrogen Bonded Binary Liquid Crystal Complex from 4-Methoxycinnamic Acid and 4-Hexyloxybenzoic Acid (4MCA:6OBA)

Abstract Hydrogen bonded liquid crystal (HBLC) binary mixture has been synthesized from mesogenic 4-methoxycinnamic acid (4MCA) and mesogenic 4-hexyloxybenzoic acid (6OBA) with different mole ratio. The mesomorphic phase behavior and corresponding phase transition temperatures along with the enthalpy values were investigated by differential scanning calorimetry (DSC). The characteristic textures of 4MCA+6OBA binary mixture were observed by using polarizing optical microscope (POM). Fourier transform infrared spectroscopic (FT-IR) studies confirm the formation of hydrogen bond in the present binary mixture. A note worthy observation in this complex is that pure mesogens have no smectic phase where as 4MCA+6OBA binary mixture exhibits a nematic phase along with higher order smectic C (Sm C) phase. Variation of mole ratio influences thermal properties such as phase peak, enthalpy values and thermal span width of the present HBLC binary mixture complex. The optical tilt angle of 4MCA+6OBA for smectic C phase and thermal stability factors have been investigated. Optical tilt angle for smectic C phase is determined and same is fitted to a power law.

Observation of induced new smectic phase in supramolecular hydrogen bonded liquid crystals between mesogenic and non-mesogenic aliphatic compounds

ABSTRACTPresent supramolecular hydrogen bonded liquid crystal (HBLC) complex is obtained between mesogenic 4-nonyloxybenzoic acid (9OBA) and non-mesogenic citric acid (CA). A phase transition temperature and enthalpy values are calculated by differential scanning calorimetry (DSC) and phase behaviour are identified by polarizing optical microscope (POM). The liquid crystal parameters and structure are characterized by POM, DSC, FT-IR, NMR and optical tilt angle studies. The DSC and POM reveals the smectic and nematic phase transitions in the present complex. The molecular structure of HBLC complex is elucidated by Proton Nuclear Magnetic Resonance (1H NMR). The noteworthy in the present complex is the nematic and Smectic C phase is separated by a Smectic X phase which shows the finger print textures. The Smectic X phase is estimated by varying the mole ratio of the CA+9OBA from 1:1 to 1:3. Molecular tilt with respect to the director the Smectic X and Smectic C phase data are fitted to a power law equation in the optical tilt angle studies and it follows the Mean Field Theory. The 1:2 mole ratio of CA+9OBA shows monotropic Smectic C phase. Another creditable observation is that while the mole ratio of 9OBA mesogenic compound increases the nematic range also increases in the present HBLC complex.

Experimental investigation on the effect of mesogenic ratio in hydrogen-bonded liquid crystal complexes

ABSTRACTHydrogen-bonded liquid crystal complex (HBLC) is synthesized from mesogenic 4-hexyloxy benzoic acid (6OBA) and aliphatic non-mesogenic citric acid (CA). The presence of intermolecular hydrogen bond in the HBLC complex is confirmed by FTIR spectrum. Phase transition temperature and enthalpy values are identified using different techniques. Induced highly ordered smectic G phase has been noticed in the present HBLC complex. Thermal span width and thermal stability factor of the individual mesogenic phase are discussed. The complexes are synthesized in different mole ratios, and their corresponding influence on the phase transitions is also discussed.

New phosphorescent platinum(ii) complexes with tetradentate C*N^N*C ligands: liquid crystallinity and polarized emission.

New phosphorescent, liquid crystalline cyclometalated tetradentate platinum complexes (Pt-L16, Pt-L12 and Pt-L6) based on the tetradentate C*N^N*C ligands (C*N^N*C = 6,6'-bis(4-(alkoxy)-phenoxy)-2,2'-bipyridine) are designed and synthesized. Their crystal structure, and photophysical, electrochemical and liquid crystal characteristics were investigated. The X-ray structure of Pt-L12 shows a severe distortion of this complex towards a tetrahedral geometry. All complexes are emissive both in degassed solution and in the solid state at room temperature with emission maxima in the red region of the spectrum. Pt-L16 and Pt-L12 show monotropic smectic liquid crystal characteristics. Moreover, these liquid crystal complexes can be aligned on a rubbed nylon-6 glass substrate and produce polarized emission with a dichroic ratio of 5.1.

The unique physical properties of the hydrogen bonded in dimers liquid crystals

The dimerization of aromatic carboxylic acids, is the base of the structure formation of hydrogen bonded in dimers liquid crystals (HBDLCs), that exhibit non-conventional mesomorphism. The structural units of these LCs are amphiphilic-type molecules, which after suitable functionalization, induce supramolecular complexes, nanocomposites based on HBDLCs. The liquid crystalline character of the nanocomposites strongly dependent on intermolecular hydrogen bonds between symmetric, where the H-donors and H acceptors are contained in similar and non-symmetric HBDLCs, where the H-donors and H acceptors are contained in unlike molecules. The strength and non-covalent character of the hydrogen bonds provides both sufficient HBDLCs complex stability and bonding flexibility with a possibility to design and drive the supramolecular geometry. We investigated a series of nanocomposites produced by mixture of HBDLC (p-n-alkyloxybenzoic acid - nOBA), serving as matrices, with non-mesogenic (single walled carbon nanotubes - SWCNTs, hydroxypiridine – HOPY) and mesogenic (cholesteryl benzoate - ChB) nano-particles in various shapes and sizes. A set of new chiral ferroelectric phases were found in the nanocomposites, otherwise do not appearing in the pristine achiral HBDLCs materials. A molecular model of an unique low-temperature ferroelectric smectic phase C based on the molecular dimer ring symmetry reduction (bent dimer formation) towards to the lowest triclinic one is presented for both symmetric and nonsymmetric supramolecular liquid crystal complexes.

Dielectric properties of nematic liquid-crystal complex based gadolinium

Dielectric properties of nematic liquid-crystal complex based gadolinium

The anisotropic properties of a terbium-based liquid crystal complex

The anisotropic properties of a terbium-based liquid crystal complex

Optical, Thermal Studies on Binary and Ternary Hydrogen-Bonded Liquid Crystal Complexes

Hydrogen-bonded ferroelectric liquid crystalline (HBFLC) complexes are synthesized from binary mixtures of l-(+)-tartaric acid with 4-dodecyloxybenzoic acid and cholesteryl acetate. A ternary complex has been obtained from l-(+)-tartaric acid, 4-dodecyloxybenzoic acid, and cholesteryl acetate. Fourier transform infrared spectroscopy (FTIR) studies confirm the formation of an intermolecular hydrogen bond in the binary as well as the ternary complex. The l-(+)-tartaric acid does not show any mesomorphic behavior, but the hydrogen-bonded binary and ternary complexes are exhibiting the nematic phase along with tilted smectic phases. Phase transition properties of HBFLC mixtures have been investigated by means of differential scanning calorimetry (DSC) and polarizing optical microscope (POM). The DSC and POM clearly reveal the existence of nematic and smectic phases in the HBFLC mixtures. The optical tilt angle of binary and ternary mixtures for smectic C* phase and thermal stability factors of the mesogenic phases have been discussed. The noteworthy observation is that there is a significant reduction of phase transition temperatures with enhanced phase width, lowering melting temperature, and clearing point in the HBFLC ternary complex.

Linear Double Hydrogen-bonded Thermotropic Liquid Crystals Formed Between Oxaloacetic Acid and p-n- Alkyloxy Benzoic Acids

ABSTRACTDouble hydrogen-bonded thermotropic liquid crystal complexes (DHBLC) have been isolated from molar ratios of Oxaloacetic acid (OAC) and eight alkyloxy benzoic acids (nBAO) whose carbon number varied from pentyloxy to dodecyloxy. The complexes are referred as OAC+nBAO where n varied from 5 to 12. In each of the synthesized complexes, complementary hydrogen bonds formed are confirmed by FTIR study and the complexes are further investigated by Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) for the construction of phase diagram. Characteristic phases like nematic, smectic C, smectic F, and smectic G are characterized by various textures. From DSC studies, odd–even effect is evinced in transition temperatures across isotropic to nematic phase transition and across smectic F to smectic G phase transition in enthalpy values. The order of all transitions observed in eight complexes is calculated by thermal analysis. The magnitude of optical tilt angle in smectic C is fitted to a power law and the scale of critical exponent is found to concur with the Mean Field theory predicted value.

Hydrogen-bonded bent-core blue phase liquid crystal complexes containing various molar ratios of proton acceptors and donors

The molar ratio, alkyl chain length, lateral fluoro-substitution and the chiral center of H-bonded bent-core supramolecules would affect the BP ranges of BPLC complexes. H-bonded bent-core complex PIIIC9/AIIF* (3/7 mol mol−1) displayed the widest BPI range of ΔTBPI = 12 °C.

Dielectric and magnetic anisotropy of a nematic ytterbium complex

The sign and the magnitude of the dielectric anisotropy of an ytterbium-based paramagnetic nematic liquid crystal complex, namely, tris[1-(4-(4-propylcyclohexyl)phenyl)octane-1,3-dione]-[5,5'-di(heptadecile)-2,2'-bipyridine]ytterbium, are determined. The temperature dependence of the permittivity components of the complex is obtained in the temperature range of a nematic phase. The sign of the anisotropy of the magnetic susceptibility of this compound is experimentally determined.

English

In this paper, thermo optical properties of homologous series of hydrogen bonded liquid crystals: p-n alkyl benzoic acid (nBA): heptyl p - hydroxybenzoate (7HB) (where n=5 to 10) have been investigated by means of applying Image analysis technique in conjunction with Polarizing Optical Microscope. Textures of liquid crystal complexes are captured. The changes in textural features as a function of temperature are useful to compute the thermo optical properties. These microscopic textures are analysed using MATLAB software. The investigated thermo optical parameters are optical transmission, Absorption coefficient, Phase retardation, birefringence and order parameter. Experimentally, this is a simple technique to observe the behaviour of the optical parameters of different liquid crystals as a function of temperature

Synthesis and study of hybrid hydrogen-bonded bent-core liquid crystal complexes containing C60- and Si-based proton donors

Mesophasic and electro-optical properties can be manipulated via the ratio of Si- and C60-based moieties in H-bonded bent-core LC complexes.

Dielectric properties of an ytterbium-based nematic liquid-crystal complex

The dielectric properties of an yttrium-based paramagnetic thermotropic nematic liquid-crystal complex have been studied. The conditions for the measurement of the magnitude and sign of the dielectric anisotropy of the mesophase have been determined. The relaxation of the components of the relative permittivity of a macroscopically homogeneously oriented sample has been observed. A high polarity of the metallomesogenic complex has been revealed.

Optimization of the Power Conversion Efficiency of Room Temperature‐Fabricated Polymer Solar Cells Utilizing Solution Processed Tungsten Oxide and Conjugated Polyelectrolyte as Electrode Interlayer

The utilization of a conjugated polyelectrolyte‐ionic liquid crystal (CPE‐ILC) complex as electron transporting layer (ETL) to improve the compatibility between the ITO and hydrophobic active layer and to promote the dipole orientation at cathode interface is reported. Simultaneously, a hole transporting layer (HTL) of solution processed tungsten oxide together with poly(2,6‐bis(trimethyltin)‐4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐4,6‐Dibromo‐thieno[3,4‐b]thiophene‐2‐carboxylic acid 2‐[2‐(2‐methoxy‐ethoxy)‐ethoxy]‐ethyl ester) (PBDTT‐TT‐TEG) efficiently shifts the work function of Ag electrode in this device. The interfacial modification of these interlayers achieves energy alignment at both electrodes. The power conversion efficiency (PCE) of the PSC based on ITO/PFN‐CbpSO/PBDTTT‐C‐T:PC70BM/PBDTT‐TT‐TEG/WO3/Ag with solution processed interlayers reaches to 7.8%. It is worthy to note that except for the electrodes, all layers of device are fabricated by solution process at room temperature and without annealing. In the case of incorporating ZnO layer into this device, the device efficiency further increases to 8.5%, which is the best value reported from PBDTTT‐C‐T:PC70BM‐based solar cells with solution processed interlayers at both electrodes so far.

Self-Assembled Conjugated Polyelectrolyte–Ionic Liquid Crystal Complex as an Interlayer for Polymer Solar Cells: Achieving Performance Enhancement via Rapid Liquid Crystal-Induced Dipole Orientation

A simple approach was demonstrated to manipulate dipole moment of interlayer in polymer solar cells (PSCs). The ionic liquid crystals (ILCs) 3-((2′-(4″-cyanobiphenyl-4-yloxy)ethyl)dimethylammonio)propanesulfonate (CbpNSO) with zwitterionic charges were blended with cationic conjugated polyelectrolyte (CPE) poly[3-(6-trimethylammoniumhexyl)thiophene] (PTNBr) to afford a novel CPE–ILC complex. The water/alcohol solubility of the CPE–ILC complex enables it to be green solvent processable. The spontaneous orientation of liquid crystal (LC) favors more ordered structural arrangement in CPE–ILC complexes. More importantly, LC-assistant assembly improves the orientation of dipole at cathode and significantly reduces the work function of ITO. The power conversion efficiency (PCE) of P3HT:PC60BM-based inverted PSCs with the layer of PTNBr–CbpNSO is increased by 37% with respect to that of the device with pure PTNBr. Incorporation of PTNBr–CbpNSO into the devices based on PBDTTT-C-T and PC71BM affords a notable PCE of 7.49%. It should be noted that mesogens reduce the activation energy of molecular reorganization and accelerate dipole orientation in CPE–ILC interlayer under external electric field, which enables the dipole of this interlayer can be readily manipulated. Because of the rapid orientation of the dipole, PTNBr–CbpNSO shows reversible dipole at the active layer/ITO interface during the reversible bias process.

Inductive effect for the phase stability in hydrogen bonded liquid crystals, x-(p/m)BA:9OBAs

A new series of hydrogen bonded liquid crystal (HBLC) complexes, made up with substituted benzoic acids (BAs) and nonyloxy benzoic acid, viz., x-(p/m)BA:9OBAs are reported for x = F, Cl, Br and –CH3 substituted at para (p) or meta (m) positions of BA moiety. Proton nuclear magnetic resonance (1H-NMR) spectrum confirms the HBLC complex. Infra red (IR) spectrum confirms linear, double and complementary type of hydrogen bonding (HB) between x-(p/m)BAs and 9OBA. The liquid crystal (LC) phases are characterised by polarisation optical microscopy (POM) and differential scanning calorimetry (DSC) techniques. x-(p/m)BA:9OBA exhibit N, C and G LC phase variance. HB induces tilted phases and enhances LC phase stability. The influence of configuration, size, electronegativity, electron directing capacity and inductive nature of substituent (x) is investigated for the stability of LC phases. An overview of the LC phase data indicates predominant ‘negative inductive effect’ in HBLCs with electron withdrawing substituents. Inductive effect operates effectively for para substitutions. Results are discussed in the wake of reports in other HBLCs.

Stepwise magnetic behavior of the liquid crystal iron(III) complex

EPR and Mossbauer spectroscopy is used to study a new liquid crystal complex of iron(III) with a Schiff base: 4,4′-dodecyloxybenzoyloxybenzoyl-4-oxysalicylidene-2-aminopyridine with a PF6− counterion. It is shown that Fe(III) ions exist only in the high-spin (HS, S = 5/2) state. It is found that under the influence of temperature the system demonstrates the stepwise behavior of the product of the integrated intensity of EPR lines (I) and temperature (proportional to χT, where χ is the magnetic susceptibility) with an inflection point at ∼80 K. Above 80 K a new EPR spectrum is detected due to the excited S = 2 state and the formation of dimeric molecules (through oxygen bridges) with a strong intramolecular antiferromagnetic exchange interaction J1 = 162.1 cm−1. Below 80 K iron(III) complexes are organized in 1D chains where the exchange value J2 = 2.1 cm−1. At 80 K there is a structural phase transition in the system: the transition from a 1D chain organization of HS Fe(III) centers to dimeric molecules. Based on quantum chemical calculations a model of the binuclear iron(III) complex is proposed.

Conformational studies of intermolecular hydorgen bonding through induced crystal G phase in nBA:7HB

This paper exploits the physical investigation on liquid crystal complexes obtained by self-organisation of p-n-alkyl benzoic acid (nBA) mesogens with non-mesogenic materials heptyl p-hydroxy benzoate (7HB). Intermolecular interactions of the molecules result the hydrogen bond between the proton donor (COOH) of nBA and proton acceptor (OH) of 7HB. The formation of hydrogen bond is attributed to the quenching of the nematic phase and inducement of crystal G phase in liquid crystal complex. A comparative study of phase abundance is presented with respect to the pure nBAs and other hydrogen bonded liquid crystal complexes of nBAs. Thermal and phase behaviour of the complexes are determined by polarising optical microscope (POM), differential scanning calorimetry (DSC) and image moments approach. Intermolecular interactions which result the hydrogen bond in complexes are investigated using Fourier transform infrared (FTIR) spectroscopy. Molecular structure of the liquid crystal complexes in the solid phase was elucidated using powder X-ray diffraction and proton nuclear magnetic resonance (1HNMR).