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Author

D. S. Shankar Rao

Other affiliations: Hungarian Academy of Sciences
Bio: D. S. Shankar Rao is an academic researcher from Raman Research Institute. The author has contributed to research in topics: Liquid crystal & Mesophase. The author has an hindex of 28, co-authored 184 publications receiving 3148 citations. Previous affiliations of D. S. Shankar Rao include Hungarian Academy of Sciences.


Papers
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Journal ArticleDOI
TL;DR: The use of Zincke reaction is reported for the first time to fabricate, under either solvothermal or microwave conditions, a viologen-linked covalent organic network in the form of hollow particles or nanosheets, which is stable in acidic, neutral, and basic aqueous solutions.
Abstract: Morphology influences the functionality of covalent organic networks and determines potential applications. Here, we report for the first time the use of Zincke reaction to fabricate, under either solvothermal or microwave conditions, a viologen-linked covalent organic network in the form of hollow particles or nanosheets. The synthesized materials are stable in acidic, neutral, and basic aqueous solutions. Under basic conditions, the neutral network assumes radical cationic character without decomposing or changing structure. Solvent polarity and heating method determine product morphology. Depending upon solvent polarity, the resulting polymeric network forms either uniform self-templated hollow spheres (HS) or hollow tubes (HT). The spheres develop via an inside-out Ostwald ripening mechanism. Interestingly, microwave conditions and certain solvent polarities result in the formation of a robust covalent organic gel framework (COGF) that is organized in nanosheets stacked several layers thick. In the gel phase, the nanosheets are crystalline and form honeycomb lattices. The use of the Zincke reaction has previously been limited to the synthesis of small viologen molecules and conjugated viologen oligomers. Its application here expands the repertoire of tools for the fabrication of covalent organic networks (which are usually prepared by dynamic covalent chemistry) and for the synthesis of viologen-based materials. All three materials-HT, HS, and COGF-serve as efficient adsorbents of iodine due to the presence of the cationic viologen linker and, in the cases of HT and HS, permanent porosity.

195 citations

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TL;DR: Pentacenequinone derivative 3 works as sensitive chemosensor for picric acid and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.
Abstract: Pentacenequinone derivative 3 forms luminescent supramolecular aggregates both in bulk as well as in solution phase. In bulk phase at high temperature, long-range stacking of columns leads to formation of stable and ordered columnar mesophase. Further, derivative 3 works as sensitive chemosensor for picric acid (PA) and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.

187 citations

Journal ArticleDOI
TL;DR: The columnar mesophase as mentioned in this paper is characterized by a structure in which the disc shaped molecules are stacked one on top of the other to form columns, the different columns constituting a two-dimensional lattice.
Abstract: Since the discovery of discotic liquid crystals in 1977 [1] the field has grown rapidly with an estimated 3000 compounds belonging to this category. Generally these compounds have flat or nearly flat cores and surrounded by four to eight long chain substituents. A vast majority of these compounds exhibit the columnar mesophase. This phase is characterized by a structure in which thedisc shaped molecules are stacked one on top of the other to form columns, the different columns constituting a two-dimensional lattice. Several variants of the columnar structure have been identified-upright columns, tilted columns, hexagonal lattice, rectangular lattice, etc. The stacking of the discs within the column could be on the one extreme, liquid-like or on the other have a true long range order. Although X-ray measurements on quite a few compounds exhibiting these different structures have been reported, the temperature dependence of the various structural parameters does not seem to have received much attention. We ...

88 citations

Journal ArticleDOI
TL;DR: In this paper, a new class of blue light emitting liquid crystalline star-shaped molecules based on 1,3,4-thiadiazoles have been designed and synthesized.
Abstract: A new class of blue light emitting liquid crystalline star-shaped molecules based on 1,3,4-thiadiazoles have been designed and synthesized. These compounds were investigated using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction, cyclic voltammetry and photophysical studies. In comparison to their 1,3,4-oxadiazole counterparts, these thiadiazole-based molecules are promising as they stabilize the hexagonal columnar phases over a broad thermal range. The thermal behavior and photophysical properties of these new star-shaped molecules are extremely dependent on the number and types of peripheral tails in the molecular structure. 1,3,4-Thiadiazole derivatives exhibit sky-blue emission in solution, unlike the deep blue emission of 1,3,4-oxadiazole derivatives. They also exhibit a lower band gap as compared to their oxadiazole counterparts and offer great potential in organic light emitting diode applications.

80 citations

Journal ArticleDOI
TL;DR: A new class of discotics derived from tris(N-salicylideneaniline)s have been synthesized and their thermal and photophysical properties are investigated, and the blue light emission has been evidenced for the former state.
Abstract: A new class of discotics derived from tris(N-salicylideneaniline)s have been synthesized and their thermal and photophysical properties are investigated. These systems with outer 1,3,4-oxadiazole wings exist in an inseparable mixture of two keto-enamine tautomeric forms with C3h and Cs rotational symmetries, and self-assemble into fluid columnar phase over a wide thermal range as evidenced by several complementary studies. They possess emissive characteristics in both solution and columnar states; the blue light (λ = 474 nm) emission has been evidenced for the former state.

79 citations


Cited by
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01 Feb 1995
TL;DR: In this paper, the unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio using DFT, MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set.
Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

1,652 citations

Journal ArticleDOI
TL;DR: A comprehensive review of the COF field is targeted, providing a historic overview of the chemistry, the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, and scrutinize the development and potential of various functions through elucidating structure-function correlations.
Abstract: Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

1,447 citations

Journal ArticleDOI
TL;DR: This critical review covers various aspects of recent research on discotic liquid crystals, in particular, molecular design concepts, supramolecular structure, processing into ordered thin films and fabrication of electronic devices.
Abstract: Discotic (disc-like) molecules typically comprising a rigid aromatic core and flexible peripheral chains have been attracting growing interest because of their fundamental importance as model systems for the study of charge and energy transport and due to the possibilities of their application in organic electronic devices. This critical review covers various aspects of recent research on discotic liquid crystals, in particular, molecular design concepts, supramolecular structure, processing into ordered thin films and fabrication of electronic devices. The chemical structure of the conjugated core of discotic molecules governs, to a large extent, their intramolecular electronic properties. Variation of the peripheral flexible chains and of the aromatic core is decisive for the tuning of self-assembly in solution and in bulk. Supramolecular organization of discotic molecules can be effectively controlled by the choice of the processing methods. In particular, approaches to obtain suitable macroscopic orientations of columnar superstructures on surfaces, that is, planar uniaxial or homeotropic alignment, are discussed together with appropriate processing techniques. Finally, an overview of charge transport in discotic materials and their application in optoelectronic devices is given (234 references).

1,278 citations