scholarly journals Effect of Fluoroalkyl-Substituent in Bistolane-Based Photoluminescent Liquid Crystals on Their Physical Behavior

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 450
Author(s):  
Shigeyuki Yamada ◽  
Yizhou Wang ◽  
Masato Morita ◽  
Qingzhi Zhang ◽  
David O’Hagan ◽  
...  
Keyword(s):  
Liquid Crystals ◽  
Alkyl Chain ◽  
Smectic Phase ◽  
Systematic Evaluation ◽  
Flexible Chain ◽  
Dynamic Changes ◽  
Unit Structure ◽  
Deep Blue ◽  
Fluoroalkyl Substituent ◽  
Significant Attention

Photoluminescent liquid crystals (PLLCs) have attracted significant attention owing to their broad applicability in thermosensing and PL switching. Extensive efforts have been made to develop bistolane-based PLLCs containing flexible units at both molecular terminals, and it has been revealed that their PL behavior can switch with the phase transition between the crystalline and LC phases. Although slight modulation of the flexible unit structure dramatically alters the LC and PL behaviors, few studies into the modification of the flexible units have been conducted. With the aim of achieving dynamic changes in their physical behaviors, we developed a family of bistolane derivatives containing a simple alkyl or a fluoroalkyl flexible chain and carried out a detailed systematic evaluation of their physical behaviors. Bistolanes containing a simple alkyl chain showed a nematic LC phase, whereas switching the flexible chain in the bistolane to a fluoroalkyl moiety significantly altered the LC phase to generate a smectic phase. The fluoroalkyl-containing bistolanes displayed a stronger deep blue PL than their corresponding non-fluorinated counterparts, even in the crystalline phase, which was attributed to the construction of rigid molecular aggregates through intermolecular F···H and F···F interactions to suppress non-radiative deactivation.

scholarly journals Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Debashis Majhi ◽  
Sergey V. Dvinskikh
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Liquid Crystals ◽  
Bond Order ◽  
Van Der Waals ◽  
Orientational Order ◽  
Smectic Phase ◽  
Side Chains ◽  
Dicationic Ionic Liquid ◽  
Ionic Liquid Crystals

AbstractIonic liquids crystals belong to a special class of ionic liquids that exhibit thermotropic liquid-crystalline behavior. Recently, dicationic ionic liquid crystals have been reported with a cation containing two single-charged ions covalently linked by a spacer. In ionic liquid crystals, electrostatic and hydrogen bonding interactions in ionic sublayer and van der Waals interaction in hydrophobic domains are the main forces contributing to the mesophase stabilization and determining the molecular orientational order and conformation. How these properties in dicationic materials are compared to those in conventional monocationic analogs? We address this question using a combination of advanced NMR methods and DFT analysis. Dicationic salt 3,3′-(1,6-hexanediyl)bis(1-dodecylimidazolium)dibromide was studied. Local bond order parameters of flexible alkyl side chains, linker chain, and alignment of rigid polar groups were analyzed. The dynamic spacer effectively “decouples” the motion of two ionic moieties. Hence, local order and alignment in dicationic mesophase were similar to those in analogous single-chain monocationic salts. Bond order parameters in the side chains in the dicationic smectic phase were found consistently lower compared to double-chain monocationic analogs, suggesting decreasing contribution of van der Waals forces. Overall dication reorientation in the smectic phase was characterized by low values of orientational order parameter S. With increased interaction energy in the polar domain the layered structure is stabilized despite less ordered dications. The results emphasized the trends in the orientational order in ionic liquid crystals and contributed to a better understanding of interparticle interactions driving smectic assembly in this and analogous ionic mesogens.

scholarly journals Influence of alkyl chain length and fluorine atoms substitution on infrared spectra of chiral liquid crystalline esters

2017 ◽  
Vol 66 (3) ◽  
pp. 63-74
Author(s):  
Anna Drzewicz ◽  
Marzena Tykarska ◽  
Magdalena Żurowska
Keyword(s):  
Molecular Structure ◽  
Infrared Spectroscopy ◽  
Liquid Crystals ◽  
Infrared Spectra ◽  
Crystalline Phase ◽  
Liquid Crystalline ◽  
Alkyl Chain ◽  
Alkyl Chain Length ◽  
Rigid Core ◽  
Helicoidal Structure

The infrared spectra were registered for series of three-ring liquid crystalline esters, differing in the structure of alkyl chain, in the substitution of benzene ring by fluorine atoms and in the type of helicoidal structure in the chiral smectic CA phase with antiferroelectric properties. The influence of molecular structure on the shift of signals coming from carbonyl group, located in the rigid core, was observed. Keywords: liquid crystals, helicoidal structure, chiral smectic CA phase, antiferroelectric crystalline phase, infrared spectroscopy

Microphase-separated multicontinuous phase in low-molecular-mass thermotropic liquid crystals

2009 ◽  
Vol 81 (10) ◽  
pp. 1783-1798 ◽  
Author(s):  
Kazuya Saito
Keyword(s):  
Liquid Crystals ◽  
Thermodynamic Potential ◽  
Alkyl Chain ◽  
Configurational Entropy ◽  
Lyotropic Liquid Crystals ◽  
Chemical Thermodynamics ◽  
Molecular Core ◽  
Thermotropic Liquid Crystals ◽  
Simple Systems ◽  
Insight Into

Extensive application of chemical thermodynamics to exotic aggregation formed in thermotropic liquid crystals is briefly described. Through thermodynamic analyses and considerations of experimental results on liquid crystals, the unexpected sharing of common properties by thermo- and lyotropic liquid crystals is demonstrated. In some thermotropic liquid crystals, the terminal alkyl chain attached to the molecular core is highly disordered, as indicated by the magnitude of configurational entropy. The molten chain serves as intramolecular solvent (self-solvent), as evidenced by the close similarity between phase diagrams against chain length and composition in the binary system with n-alkane. These facts lead to the quasi-binary picture of thermotropic liquid crystals. Consideration of the thermodynamic potential expanded in terms of density fluctuation gives a new insight into the multicontinuous phases formed in simple systems consisting of anisotropic, rodlike particles.

Photo-induced guest-host interactions produce chiral conglomerates accompanying grain boundaries in a smectic phase

2021 ◽  
Author(s):  
Hideaki Sasaki ◽  
Koudai Abe ◽  
Masanobu Sagisaka ◽  
Atsushi Yoshizawa
Keyword(s):  
Phase Transition ◽  
Liquid Crystals ◽  
Physical Properties ◽  
Grain Boundaries ◽  
Smectic Phase ◽  
Host Interactions

Photo-induced isomerization of an azobenzene unit not only induces phase transition between two different phases but also brings marked changes of physical properties in solids and liquid crystals. We prepared...

scholarly journals Synthesis and Characterization of Photoluminescence Liquid Crystals Based on Flexible Chain-Bearing Pentafluorinated Bistolanes

Crystals ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 603
Author(s):  
Shigeyuki Yamada ◽  
Masaya Sato ◽  
Tsutomu Konno
Keyword(s):  
Phase Transition ◽  
Liquid Crystals ◽  
Oxygen Atom ◽  
Liquid Crystalline ◽  
Color Change ◽  
Photophysical Properties ◽  
Structure Property ◽  
Flexible Chain ◽  
Structure Property Relationships ◽  
Chiral Nematic

The liquid-crystalline (LC) and photophysical properties of molecules are very sensitive to their electronic and molecular aggregate structures. Herein, to shed light on the structure–property relationships of pentafluorinated bistolane-based photoluminescence (PL) liquid crystals (PLLCs) previously reported by our group, we synthesized pentafluorinated bistolanes with variable flexible chains and evaluated their LC and photophysical properties. The incorporation of an oxygen atom (to afford a 2-methoxyethoxy unit) or an oxygen atom and a methyl group (to afford a 1-methoxyprop-2-oxy unit) into the flexible butoxy chain significantly decreased the temperature of the crystalline-to-LC phase transition, and a chiral nematic phase comprising helical molecular aggregates was observed for the chiral 1-methoxyprop-2-oxy group–bearing bistolane. The synthesized bistolanes exhibited strong blue PL in both solution and crystalline phases; the featuring PL characteristics were maintained in the LC phase (produced by the crystalline-to-LC phase transition) except for a slight PL color change. Thus, it was concluded that the PL behavior of pentafluorinated bistolanes can be modulated by the choice of a suitable flexible chain, and the obtained insights are believed to facilitate the application of PLLCs in thermosensing PL materials.

Synthesis and Mesomorphic Properties of New Liquid Crystalline Cyclohexyl-phenyl- and Dicyclohexyl-pyrimidines

1979 ◽  
Vol 34 (11) ◽  
pp. 1535-1541 ◽  
Author(s):  
Alois Villiger ◽  
Arthur Boiler ◽  
Martin Schadt
Keyword(s):  
Liquid Crystals ◽  
Liquid Crystalline ◽  
Alkyl Chain ◽  
Viscosity Reduction ◽  
Refractive Indices ◽  
Thermal Compatibility ◽  
Chain Lengths ◽  
New Compounds ◽  
Mesomorphic Properties ◽  
End Group

Abstract Liquid Crystals, Cyclohexyl-phenyl-pyrimidines, Dicyclohexyl-pyrimidines The synthesis and mesomorphic properties of three new classes of cyano-substituted cyclohexyl-phenyl-and dicyclohexyl-pyrimidines are reported. The compounds are colourless, chemically and photochemically stable and have wide nematic mesophases. The thermal compatibility of the new compounds with other nematic liquid crystals is excellent. The large static positive dielectric anisotropics are shown to depend strongly on the position and number of hydrogenated rings as well as on the alkyl chain lengths within a homologous series. The reported bulk viscosities vary considerably among homologues. Hydrogenating the ring adjacent to the cyano end group causes η to increase, whereas a considerable viscosity reduction compared to nonhydrogenated homologues was found by hydrogenating the ring adjacent to the alkyl end group. The measured refractive indices of the new compounds are comparable to those of biphenyls.

scholarly journals Design of Ionic Liquid Crystals Forming Normal-Type Bicontinuous Cubic Phases with a 3D Continuous Ion Conductive Pathway

Crystals ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 309 ◽  
Author(s):  
Takahiro Ichikawa ◽  
Yui Sasaki ◽  
Tsubasa Kobayashi ◽  
Hikaru Oshiro ◽  
Ayaka Ono ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Liquid Crystals ◽  
Ionic Conductivity ◽  
Liquid Crystalline ◽  
Alkyl Chain ◽  
Normal Type ◽  
Ion Conduction ◽  
Cubic Phases ◽  
Bicontinuous Cubic ◽  
Chain Lengths

We have prepared a series of pyridinium-based gemini amphiphiles. They exhibit thermotropic liquid–crystalline behavior depending on their alkyl chain lengths and anion species. By adjusting the alkyl chain lengths and selecting suitable anions, we have obtained an ionic amphiphile that exhibits a normal-type bicontinuous cubic phase from 38 °C to 12 °C on cooling from an isotropic phase. In the bicontinuous cubic liquid–crystalline assembly, the pyridinium-based ionic parts align along a gyroid minimal surface forming a 3D continuous ionic domain while their ionophobic alkyl chains form 3D branched nanochannel networks. This ionic compound can form homogeneous mixtures with a lithium salt and the resultant mixtures keep the ability to form normal-type bicontinuous cubic phases. Ion conduction measurements have been performed for the mixtures on cooling. It has been revealed that the formation of the 3D branched ionophobic nanochannels does not disturb the ion conduction behavior in the ionic domain while it results in the conversion of the state of the mixtures from fluidic liquids to quasi-solids, namely highly viscous liquid crystals. Although the ionic conductivity of the mixtures is in the order of 10–7 S cm–1 at 40 °C, which is far lower than the values for practical use, the present material design has a potential to pave the way for developing advanced solid electrolytes consisting of two task-specific nanosegregated domains: One is an ionic liquid nano-domain with a 3D continuity for high ionic conductivity and the other is ionophobic nanochannel network domains for high mechanical strength.

Smectic Phase Exhibited by Dissymmetric Liquid Crystals: Effect of a Terminal Fluoromethyl Group on Mesomorphic Properties

2002 ◽  
Vol 276 (1) ◽  
pp. 83-92 ◽  
Author(s):  
Takeyasu Tasaka ◽  
Shunsuke Takenaka ◽  
Koji Kabu ◽  
Yuki Morita ◽  
Hiroaki Okamoto
Keyword(s):  
Liquid Crystals ◽  
Smectic Phase ◽  
Mesomorphic Properties
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