The synthesis and study of the photo- and thermoresponsive behavior of a series of novel asymmetric mesogenic dimers, consisting of a cholesterol moiety linked to a diphenylbutadiene chromophore via flexible alkyl chains are reported. These mesogenic dimers possess the combined glass forming properties of the cholesterol moiety and the photochromic and luminescent properties of the butadiene moiety. Photoinduced cis/trans isomerization of the butadiene chromophore in these materials could be utilized to bring about an isothermal phase transition from the smectic to the cholesteric state. By photochemically controlling the cis/trans isomer ratio, the pitch of the cholesteric could be continuously varied making it possible to tune the color of the film over the entire visible region, and the color images thus generated could be stabilized by converting them to N* glasses. These materials were also polymorphic, exhibiting two crystalline forms possessing distinctly different fluorescence properties. The ability to thermally switch these materials from one crystalline form to the other in a reversible manner also makes them useful for recording fluorescent images.
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http://dx.doi.org/10.1021/ja061575k | DOI Listing |
Beilstein J Org Chem
December 2024
Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg (UMR 7504), F-67034 Strasbourg, France.
The high potential of non-covalent arene-fluoroarene intermolecular interactions in the design of liquid crystals lies in their ability to strongly promote self-assembly, improve the order and stability of the supramolecular mesophases, and enable tuneability of the optical and electronic properties, which can potentially be exploited for advanced applications in display technologies, photonic devices, sensors, and organic electronics. We recently successfully reported the straightforward synthesis of several mesogens containing four lateral aliphatic chains and derived from the classical triphenylene core self-assembling in columnar mesophases based on this paradigm. These mesogenic compounds were simply obtained in good yields by the nucleophilic substitution (SFAr) of various types of commercially available fluoroarenes with the electrophilic organolithium derivatives 2,2'-dilithio-4,4',5,5'-tetraalkoxy-1,1'-biphenyl (2Li- ).
View Article and Find Full Text PDFChemphyschem
December 2024
Polymer Science and Technology, CSIR-Central Leather Research Institute, Adyar, Chennai, 600020, India.
A Model mesogen and its symmetrical Dimer made up of phenyl benzoate core unit are investigated by C NMR spectroscopy. The existence of layer order in smectic A and smectic C phases of Dimer mesogen is established by powder X-ray diffraction. The chemical shift anisotropy (CSA) tensors of Model mesogen are determined by 2D separation of undistorted powder patterns by effortless recoupling (SUPER) experiment and are utilized for calculating the order parameters employing the alignment-induced chemical shifts (AIS).
View Article and Find Full Text PDFSoft Matter
September 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Mohali, Sector 81, Knowledge City, Manauli 140306, India.
Non-symmetrical cholesterol-based dimers have emerged as crucial materials in the field of liquid crystal research, owing to their remarkable ability to stabilize various exotic mesophases, including the blue phases (BPIII, BPII, BPI), cholesteric nematic (N*) phase, smectic blue phase (SmBP), twist grain boundary (TGB) phase, smectic A/smectic A* (SmA/SmA*) phase, and smectic C/smectic C* (SmC/SmC*) phase. These mesophases have garnered considerable attention due to their diverse applications in spatial light modulation, chiro-optical devices, optical switching, thermochromic materials, and more. In this study, we present the synthesis and comprehensive characterization of a series of non-symmetrical cholesterol-based bent-shaped dimers (1/12, 1/14, 1/16) in which the cholesterol unit is intricately linked to an aromatic mesogenic core through a flexible spacer.
View Article and Find Full Text PDFMaterials (Basel)
May 2024
Department of Physics, University of Patras, 26504 Patras, Greece.
We present a comparative study of the optical and dielectric anisotropy of a laterally fluorinated liquid crystal dimer and its homologous trimer, both exhibiting two nematic phases. In the high-temperature nematic phase, both oligomers exhibit positive optical anisotropy with similar magnitude, which, however, is lower in comparison with the optical anisotropy of the monomer. In the same temperature range, the dielectric permittivity along and perpendicular to the nematic director, measured on magnetically aligned samples, reveals negative dielectric anisotropy for both oligomers, which saturates as the temperature approaches the N-N phase transition temperature.
View Article and Find Full Text PDFSoft Matter
May 2024
Centre for Nano and Soft Matter Sciences Arkavathi, Survey No. 7, Shivanapura, Dasanapura Hobli, Bengaluru-562162, India.
Introducing restricted rotation in a molecule, often achieved through the incorporation of double or triple bonds, constitutes a crucial approach to induce a frustrated mesophase. Furthermore, the inclusion of a chiral moiety, such as cholesterol, serves to enhance the stabilization of chiral frustrated mesophases. This study presents the synthesis and characterization of novel optically active dimers incorporating cholesterol and phenyl 3-phenylpropiolate segments interconnected by an ω-oxyalkanoyloxy spacer with varying lengths and parity.
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