Design,synthesis and characterization of hydrogen bonded thermotropic liquid crystals

A homologous series of seven linear hydrogen bonded thermotropic liquid crystals are isolated from p-n-octyloxy benzoic acid (8BAO) and p-n alkyl benzoic acids (nBA, where n varies from 2 to 8). In all the seven complexes, hydrogen bonding is a result of complementary proton-donor and electron-acceptor pairs derived from carboxylic acids of 8BAO and nBA. Spectroscopic characterization such as Fourier Transform Infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (¹HNMR, ¹³CNMR) are performed for all the seven complexes to confirm the intermolecular hydrogen bonding and the nature of chemical environment respectively. Seven mesogen are examined by Polarizing Optical Microscope (POM) for identification of the phase polymorphism through standard textures. Transition temperatures and corresponding enthalpy values of the individual mesogenic phases are experimentally obtained from the analysis of the respective Differential Scanning Calorimetry (DSC) thermograms. Phase diagram of this homologous series is constructed based on the data of transition temperatures, further qualitative analysis of the phase abundance is discussed. Thermal stability factor for each of the mesogenic phase has been determined. Order of phase transition is experimentally obtained by Navard and Cox technique. Specific heat for each phase transition of individual complexes is derived from the DSC data. Change of color of the texture with temperature in the same phase is referred as parachromatism and is observed in nematic phase of two mesogens.     

Analysis of optical and thermal properties of double hydrogen bonded liquid crystal binary mixtures

Eighteen binary mixtures are prepared from three thermotropic double hydrogen bonded liquid crystal complexes formed by Mesaconic Acid (ME) and various alkyloxy benzoic acids, namely ME + 5BAO, ME + 11BAO and ME + 12BAO where 5BAO, 11BAO and 12BAO represents pentyloxy benzoic acid, undecyloxy benzoic acid and dodecyloxy benzoic acid respectively. Two sets of binary mixtures (ME + 12BAO with ME + 5BAO and ME + 11BAO with ME + 5BAO) are formed by varying their molar ratio in steps of 0.1 to 0.9 which leads to the formation of eighteen binary mixture complexes. Existence of different energy bands in the binary mixtures is identified from the analysis of Fourier Transform Infrared Spectroscopy (FTIR). Phases such as nematic and smectic C are observed in all the binary mixtures which are confirmed through Polarizing Optical Microscopy (POM). Transition temperatures corresponding to the individual mesophases are further verified using Differential Scanning Calorimetry (DSC). Phase diagram of two sets of binary mixtures are constructed with the aid of POM and DSC data. Optical tilt angle measurement; a primary order parameter; is calculated in smectic C phase of the binary mixtures and the resultant data obtained is fitted to critical exponent value is in concurrence with the Mean Field theory predicted value. Thermal studies such as stability factor, order of phase transitions and specific heat capacity value of the mesophases are extracted from the DSC thermograms.     

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

Hydrogen 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.     

Synthesis,characterization of new carboxylic acid derivatives bearing 1,3,4-thiadiazole moiety and study their liquid crystalline behaviors

Thirteen carboxylic acid derivatives containing 1,3,4-thiadiazole ring in their core and swinging alkoxy terminal were synthesized. They were characterized by ¹H, ¹³C NMR spectroscopy, FTIR, and mass spectrometry. Their liquid crystalline behaviors have been studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The 1,3,4-thiadiazole compounds in this study were 2,5 di-substituted asymmetrical, alkoxy, and carboxy linkages. The compounds with alkoxy of long carbon chains (n > 7) displayed Smectic C phase. The liquid crystal properties were found to be affected by the length of alkoxy chain attached to the phenyl moiety and the two types of the dimeric form were resulted from the hydrogen bonding interaction between carboxylic acid molecules.     

Influence of flexible chain,polar substitution and hydrogen bonding on phase stability in Shiff based (4)PyBD(4I)BrA-nOBA series of liquid crystals

Shiff based Linear Hydrogen Bonded Liquid Crystalline homologues, viz., (4)PyBD(4^I)BrA-nOBAs for n = 2,3,4,5,6,7,8,10,11 and 12 are synthesized. ¹H-NMR and ¹³C-NMR studies confirm the formation of HBLC and IR confirms the linear hydrogen bonding. Liquid crystal phase abundance, transition temperatures, enthalpy and order of transition are investigated by Polarized Optical Microscopy textural studies and Differential Scanning Calorimetry. Nematic, Smectic-A, -D, -C, B_hexatic, -B_Crystal, -F, -I and –G phases are identified. Large LC phase variances, viz., NAB_hexFG and NACFG are exhibited by intermediate chain length with n = 5 and 6. A-C transition exhibited unique II-order nature. II-order nature for G-Solid transition explained. Phase diagram drawn with flexible chain length infers INA, and ACF and CIF MultiCritical Points and Lifshitz behaviour. NA TriCiritical Point predicted in [3+7] binary. Influences of chain length, linear HB and end polar(-Br) substitution for LC phase stability are is discussed. Results of Phase stability are discussed in the wake of the body of the data and reports in other LCs. DSC enthalpy suggests for utility of intermediate and higher homologues for device savvy tilted Smectic LC phases.