Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

About Supramolecular Assemblies of π-Conjugated Systems

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

This critical review begins with a brief, but essential, introduction to the special nature of liquid crystal materials, their peculiar properties, and their commercial applications, followed by an introductory insight into the remarkable nature of the fluoro substituent, and its fascinating influence on the properties of organic compounds. However, the main focus of the review is to discuss the enormous amount of exciting research on fluorinated liquid crystals that has been reported. The small size of the fluoro substituent enables its incorporation into all types of liquid crystal, including calamitic, discotic, banana, lyotropic, and polymers, without ruining the liquid crystalline nature of the material. However the fluoro substituent is larger than hydrogen, and hence causes a significant steric effect, which combined with the high polarity, confers many fascinating, and often remarkable, modifications to melting point, mesophase morphology and transition temperatures, and the many other very important physical properties, such as dielectric anisotropy, optical anisotropy, and visco-elastic properties. There are many different positions within a liquid crystal structure where a fluoro substituent can be located, including (i) a terminal position, (ii) within a terminal chain, as a semi-fluorinated or as a perfluorinated chain, or as one fluoro substituent at a chiral centre, (iii) as part of a linking group, and (iv) a lateral position in the core section. Such variety enables the interesting and advantageous tailoring of properties, both for the fundamental purposes of establishing structure–property relationships, and for materials targeted towards commercially-successful liquid crystal display applications.

Fluorinated liquid crystals – properties and applications

Discotic Liquid Crystals.

We have calculated the diffraction of light perpendicular to the twist axis in a chiral smectic C liquid crystal. In contrast to a cholesteric liquid crystal, in a chiral smectic C liquid crystal we find extra orders which form the odd orders in the diffraction pattern. For an incident linearly polarized light, at a general azimuth, these odd orders are linearly polarized and the even orders are elliptically polarized. The intensities of the odd orders are always independent of the azimuth of the incident light, while this is possible for even orders only at a particular tilt angle of the chiral smectic C liquid crystal. Also, for the incident vibration parallel or perpendicular to the twist axis the odd orders are polarized in the orthogonal linear state with respect to incident vibration, while the even orders are in the same linear state.

Optical diffraction in twisted liquid-crystalline media-phase grating mode

Closed loop electronics for resonant sensors

We report an unusual thermal variation of the ordinary refractive index ( n o) of the nematogenic compound 2-cyano-4-heptyl-phenyl-4′-pentyl-4-biphenyl carboxylate, which has a cyano group making a large angle (~60°) with the molecular axis. As the sample is cooled from the NI transition point, n o initially decreases as usual, but on further cooling it shows an increasing trend after reaching a broad minimum. On the other hand, the extraordinary index n e shows the normal temperature variation. X-ray investigations of a monodomain sample show that the nematic has a skewed cybotactic type of short-range order, the tilt angle increasing considerably as the temperature is lowered from the NI transition point. We have made a model calculation to explain the temperature variation of n o in terms of the variation of the tilt angle.

Effect of skew cybotactic structure on the optical properties of a nematogen with a lateral cyano substituent

Electron transfer studies on cholesterol LB films assembled on thiophenol and 2-naphthalenethiol self-assembled monolayers.

We have studied films of an ionic discogenic (discotic mesogenic) molecule (pyridinium salt tethered with hexaalkoxytriphenylene (PyTp)) and DNA complex at air-water (A-W) and air-solid interfaces. We have formed an PyTp monolayer on an aqueous subphase containing a small amount of DNA to obtain a PyTp-DNA complex at the A-W interface. Compared to the pure PyTp monolayer, the PyTp-DNA complex monolayer exhibits a higher collapse pressure and lower limiting area, indicating condensation and better stability. A Brewster angle microscope was used for in situ observation of the morphology of the film at the A-W interface. The PyTp-DNA complex films on silicon wafers were prepared using the Langmuir-Blodgett (LB) technique. We find that several tens of layers of the PyTp-DNA complex monolayer can be transferred with good efficiency. Fourier transform infrared spectroscopy studies confirm the presence of DNA in the LB films of the PyTp-DNA complex. Nanoindentation measurements using atomic force microscope reveal that the PyTp-DNA complex films are about two times harder as compared to the pure PyTp films.

K. A. Suresh

Papers

Optical diffraction in twisted liquid-crystalline media-phase grating mode

Closed loop electronics for resonant sensors

Effect of skew cybotactic structure on the optical properties of a nematogen with a lateral cyano substituent

Electron transfer studies on cholesterol LB films assembled on thiophenol and 2-naphthalenethiol self-assembled monolayers.

Discogen-DNA complex films at air-water and air-solid interfaces.