Cyanines during the 1990s: A Review

Microwave assisted organic reactions

Most associate liquid crystals with their everyday use in laptop computers, mobile phones, digital cameras, and other electronic devices. However, in contrast to their rodlike (calamitic) counterparts, first described in 1907 by Vorlander, disklike (discotic, columnar) liquid crystals, which were discovered in 1977 by Chandrasekhar et al., offer further applications as a result of their orientation in the columnar mesophase, making them ideal candidates for molecular wires in various optical and electronic devices such as photocopiers, laser printers, photovoltaic cells, light-emitting diodes, field-effect transistors, and holographic data storage. Beginning with an overview of the various mesophases and characterization methods, this Review will focus on the major classes of columnar mesogens rather than presenting a library of columnar liquid crystals. Emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties. Finally, some applications and perspectives in materials science and molecular electronics will be discussed.

Discotic Liquid Crystals: From Tailor-Made Synthesis to Plastic Electronics

The application of (S)-1,10-binaphthyl-2,20-diol as NMR chiral solvating agent (CSA) for omeprazole, and three of its analogs (lanso-, panto-, and rabe-prazole) was investigated. The formation of diastereomeric host–guest complexes in solution between the CSA and the racemic substrates produced sufficient NMR signal splitting for the determination of enantiomeric excesses by Hor F-NMR spectroscopy. Using of hydrophobic deuterated solvents was mandatory for obtaining good enantiodiscrimination, thus suggesting the importance of intermolecular hydrogen bonds in the stabilization of the complexes. The method was applied to the fast quantification of the enantiomeric purity of in-process samples of S-omeprazole. Chirality 00:000–000, 2009. VC 2009

The assignment of absolute configuration by NMR

Structures and properties of liquid crystalline phases formed by bent-core molecules are reviewed. At least eight phases designated as B1–B8 have been found, being unambiguously distinguished from phases formed by usual calamitic molecules due to a number of remarkable peculiarities. In addition to B1–B8 phases, smectic A-like phases and biaxial nematic phases formed by bent-core molecules are also reviewed. The most attractive aspects of this new class of liquid crystals are in polarity and chirality, despite being formed from achiral molecules. The bent-core mesogens are the first ferroelectric and antiferroelectric liquid crystals realized without introducing chirality. Spontaneous chiral deracemization at microscopic and macroscopic levels occurs and is controllable. Moreover, achiral bent-core molecules enhance system chirality. The interplay between polarity and chirality provides chiral nonlinear optic effects. Further interesting phenomena related to polarity and chirality are also reviewed.

https://iopscience.iop.org/article/10.1143/JJAP.45.597/pdf

Bent-Core Liquid Crystals: Their Mysterious and Attractive World

The present report undertakes a challenge of general interest in supramolecular chemistry: the achievement of helical organizations with controlled structure. To achieve this target we considered the possibility of inducing supramolecular chirality using molecules that were designed to organize into columnar mesophases. The use of oxazoline-derived ligands and metal coordination served as tools to prepare molecules with a phasmidic-like structure, which show columnar organization in the liquid crystalline state. To ensure the formation of chiral mesophases, these complexes bear stereogenic centers in the rigid coordination environment of the metal. X-ray and circular dichroism experiments have revealed that chirality transfer does indeed take place from the chiral molecule to the columnar liquid crystal organization. This chiral columnar organization appears as a helix consisting of stacks of molecules that rotate with respect to one another along the column while maintaining their mean planes parallel to each other. In fact, it has been concluded that packing of these polycatenar molecules must be more efficient upon rotation of a molecule with respect to the adjacent one along the column. Furthermore, the same type of helical supraorganization has been found to be present in the mesophase of the racemic mixture and the mixture of diastereomers prepared from the racemic ligand. In this case, segregation of the optical isomers is proposed to occur to give rise to both types of helix (right-handed and left-handed).

Supramolecular helical stacking of metallomesogens derived from enantiopure and racemic polycatenar oxazolines

Chiral oxovanadium(IV), copper(II), and palladium(II) ‚-diketonates show a room-temperature columnar mesophase which undergoes ferroelectric switching. All the compounds were obtained as liquid crystals at room temperature, and crystallization or melting processes were not detected by differential scanning calorimetry carried out to -20 °C. The mesophase was investigated by optical microscopy, DSC and X-ray diffraction, and identified as a rectangular columnar ( P21). The flowerlike texture observed for all the compounds led us to deduce a high tilt angle (ca. 40°) of the molecules with respect to the column axis. Circular dichroism has confirmed the existence of a helical arrangement within the column. This result is in accordance with the so-called columnar mode found at low frequencies (ca. 10 -3 Hz) in dielectric spectroscopy studies. The electrooptical response of these materials has been examined by means of a photomultiplier. The results obtained can be explained by considering a strong influence of the high tilt angle found in the mesophase.

/pdf/switchable-columnar-metallomesogens-new-helical-self-4n934z3yfl.pdf

Switchable Columnar Metallomesogens. New Helical Self-Assembling Systems

Stereoselective synthesis of seven-membered carbocycles from 2-amino-1,3-butadienes and vinyl chromium fischer-type carbenes

The thyroid hormone and retinol transporter protein known as transthyretin (TTR) is in the origin of one of the 20 or so known amyloid diseases. TTR self assembles as a homotetramer leaving a central hydrophobic channel with two symmetrical binding sites. The aggregation pathway of TTR into amiloid fibrils is not yet well characterized but in vitro binding of thyroid hormones and other small organic molecules to TTR binding channel results in tetramer stabilization which prevents amyloid formation in an extent which is proportional to the binding constant. Up to now, TTR aggregation inhibitors have been designed looking at various structural features of this binding channel others than its ability to host iodine atoms. In the present work, greatly improved inhibitors have been designed and tested by taking into account that thyroid hormones are unique in human biochemistry owing to the presence of multiple iodine atoms in their molecules which are probed to interact with specific halogen binding domains sitting at the TTR binding channel. The new TTR fibrillogenesis inhibitors are based on the diflunisal core structure because diflunisal is a registered salicylate drug with NSAID activity now undergoing clinical trials for TTR amyloid diseases. Biochemical and biophysical evidence confirms that iodine atoms can be an important design feature in the search for candidate drugs for TTR related amyloidosis.

/pdf/iodine-atoms-a-new-molecular-feature-for-the-design-of-4oqny54hxc.pdf

Jesús T. Vázquez

Papers

Supramolecular helical stacking of metallomesogens derived from enantiopure and racemic polycatenar oxazolines

Switchable Columnar Metallomesogens. New Helical Self-Assembling Systems

Stereoselective synthesis of seven-membered carbocycles from 2-amino-1,3-butadienes and vinyl chromium fischer-type carbenes

Iodine atoms: a new molecular feature for the design of potent transthyretin fibrillogenesis inhibitors

Pairwise additivity in exciton-coupled CD curves of multichromophoric systems