About Supramolecular Assemblies of π-Conjugated Systems

: 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

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

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.

Covalent Organic Frameworks: Design, Synthesis, and Functions.

Functional π-Gelators and Their Applications

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).

Discotic liquid crystals: a new generation of organic semiconductors

A series of 2-phenylbenzoxazole liquid crystals having intramolecular hydrogen-bonded Schiff's base linkers have been synthesised. All of them exhibit liquid crystalline phase behaviour. They showed only SmC phase transition. The phase is stabilised over a wide temperature range due to the presence of intramolecular H-bonding.

2-phenylbenzoxazole-containing calamitic liquid crystals: synthesis and characterisation

We describe measurements of the permittivity and Frank elastic constant in the nematic phase of a binary system displaying a transition between the nematic (N) and the recently discovered twist-bend nematic (NTB) phase. Among the salient features observed are (i) the existence of the NTB phase even when the system is loaded with a high concentration (∼64 mol %) of a rodlike component; (ii) a clear signature in permittivity of the N–NTB transition; and (iii) a lower value of the bend elastic constant compared to the splay over a large phase space, with the difference between the two becoming a maximum for an intermediate mixture. These studies further support the surprising idea that the elastic features associated with bent molecules can be further augmented by suitable rodlike additives.

Binary System Exhibiting the Nematic to Twist-Bend Nematic Transition: Behavior of Permittivity and Elastic Constants

Recently we developed [1] a novel liquid crystal display device employing discotic nematic material. This device exhibits the following improvements over a conventional twisted nematic (TN) display device using a calamitic nematic material. The device (i) is simple to fabricate and (ii) has excellent viewing angle characteristics showing a wide and symmetric viewing angle profile, (iii) has much less difference in the pixel capacitance between the ON and OFF states resulting in reduced cross talk problem. However the response time of the device is slower than conventional TN devices. An obvious solution to this problem is to reduce the viscosity of the material. To achieve this we have doped, in small concentrations, a long chain alkane compound to the parent room-temperature discotic nematic material. Systematic studies show that both the switch ON and switch OFF response times show a significant decrease, i.e., the device switches faster, in the case of the mixtures. It should be mentioned that wide and symmetric viewing angle characteristics remain unaffected by the addition of the dopant material. However both the switch ON and switch OFF response times are still an order of magnitude slower compared to that of conventional TN devices. Considering the fact that these response times are not very different from those for the STN displays, the achievement of symmetric and wide viewing angle characteristics with a simple fabrication process makes this device quite interesting. To make them attractive enough to be considered for commercial applications new materials with faster response have to be developed. Efforts in this direction are underway in our laboratory.

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Electrooptic and viewing angle characteristics of a display device employing a discotic nematic liquid crystal

Novel photoluminescent lanthanidomesogens forming bilayer smectic phase derived from blue light emitting liquid crystalline, one ring O-donor Schiff-base ligands

A rational synthesis for dibenzo[fg,op]naphthacene derivatives (also named as dibenzopyrene) is described. The methodology involves the preparation of a quaterphenyl using a palladium-catalysed cross-coupling of arylboronic acids followed by chemical or photochemical cyclization. The versatility of the process is shown by the formation of various dibenzo[fg,op]naphthacene derivatives having identical or non-identical peripheral chains. All the new compounds exhibit a single mesophase, which has been identified by X-ray diffractometry and optical microscopy as hexagonal columnar (Colh). X-Ray results confirm that hexasubstituted dibenzonaphthacenes are more ordered than octasubstituted derivatives.

D. S. Shankar Rao

Papers

2-phenylbenzoxazole-containing calamitic liquid crystals: synthesis and characterisation

Binary System Exhibiting the Nematic to Twist-Bend Nematic Transition: Behavior of Permittivity and Elastic Constants

Electrooptic and viewing angle characteristics of a display device employing a discotic nematic liquid crystal

Novel photoluminescent lanthanidomesogens forming bilayer smectic phase derived from blue light emitting liquid crystalline, one ring O-donor Schiff-base ligands

Novel dibenzo[fg,op]naphthacene discotic liquid crystals: a versatile rational synthesis