About Supramolecular Assemblies of π-Conjugated Systems

Graphenes as potential material for electronics.

Dendron-mediated self-assembly, disassembly, and self-organization of complex systems have been investigated. The most ideal building blocks would need to display shape persistence in solution and in the solid state, since only this feature provides access to the use of complementary methods of structural analysis. Most supramolecular dendrimers are chiral even when they are constructed from nonchiral building blocks and are equipped with mechanisms that amplify chirality. This poses additional challenges associated with the understanding of the structural origin of chirality in different supramolecular structures through combinations of structural analysis methods. While many supramolecular structures assembled from dendrimers and dendrons resemble some of the related morphologies generated from block-copolymers, they are much more complex and are not determined by the volume ratio between the dissimilar parts of the molecule.

Dendron-Mediated Self-Assembly, Disassembly, and Self-Organization of Complex 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

Tetrathiafulvalene (TTF) and its derivatives were originally prepared as strong electron-donor molecules for the development of electrically conducting materials. This Review emphasizes how TTF and its derivatives offer new and in some cases little-exploited possibilities at the molecular to the supramolecular levels, as well as in macromolecular aspects. TTF is a well-established molecule whose interest goes beyond the field of materials chemistry to be considered an important building block in supramolecular chemistry, crystal engineering, and in systems able to operate as machines. At the molecular level, TTF is a readily available molecule which displays a strong electron-donor ability. However, its use as a catalyst for radical-polar crossover reactions, thus mimicking samarium iodide chemistry, has only recently been addressed. Important goals have been achieved in the use of TTF at the macromolecular level where TTF-containing oligomers, polymers, and dendrimers have allowed the preparation of new materials that integrate the unique properties of TTF with the processability and stability that macromolecules display. The TTF molecule has also been successfully used in the construction of redox-active supramolecular systems. Thus, chemical sensors and redox-switchable ligands have been prepared from TTF while molecular shuttles and molecular switches have been prepared from TTF-containing rotaxanes and catenanes. A large synthetic effort has been devoted to the preparation of the so-called organic ferromagnets, many of which are derived from TTF. The main task in these systems is the introduction of ferromagnetic coupling between the conduction electrons and localized electrons. TTF has also played a prominent role in molecular electronics where TTF-containing D-sigma-A molecules have allowed the preparation of the first confirmed unimolecular rectifier. Recently, it has been confirmed that TTF can display efficient nonlinear optic (NLO) responses in the second and third harmonic generation as well as a good thermal stability. These findings can be combined with the redox ability of TTF as an external stimuli to provide a promising strategy for the molecular engineering of switchable NLO materials. Fullerenes endowed with TTF exhibit outstanding photophysical properties leading to charge-separated (CS) states that show remarkable lifetimes.

New Concepts in Tetrathiafulvalene Chemistry.

Among the various mesogenic polyaromatic cores, only benzene, triphenylene, truxene and anthraquinone hexasubstituted derivatives exhibit one or several D columnar phases and/or a ND lenticular nematic phase. A simple scheme of nomenclature is suggested for the six different types of columnar phase requiring only two structural parameters: firstly the symmetry of the lattice (hexagonal: Dh, rectangular: Dr, oblique: Dob), and secondly the order or disorder within the column. Several examples of disc-like compounds which form phases Dho, Dhd, Drd(P21/a) , Drd(P2/a), Drd(C2/m), Dod.d are described and a discussion of the specificity of the corresponding optical textures is given. Then the complex polymorphism of these new mesogenic materials (normal, inverse, reentrant columnar-nematic sequences) is reviewed. Finally, a simple classification of the various types of lyotropic and thermotropic phase is proposed, based on the shape of the structural element (finite or infinite cylinder, disc, infinite...

Disc-Like Mesogen Polymorphism

Five mesomorphic phases are described in several disc-like liquid-crystals. They are hexalkanoyloxy benzenes, triphenylenes or truxenes, hexa-alkoxy triphenylenes, hexa-benzoates of triphenylene. Several of these compounds exhibit a complex polymorphism. Informations on the structures of these phases have been obtained by means of X-Ray diffraction; except a Nd namatic phase all the others one are columnar phases. At the same time a systematic study has been performed by the well known method of isomorphy. All these results allow us to propose a general classification of these phases.

Disc-Like Mesogens: A Classification

Two hexa-alkoxy derivatives (7a and 7b) of terephthal-bis-[4-benzoyloxyaniline] are described. They exhibit two new types of mesophase for which the term phasmidic is proposed: one has an hexagonal 2D lattice and the second an oblique 2D lattice Description de deux derives hexaalcoxy de la terephtal-bis-[benzoyloxy-4-aniline], presentent deux nouveaux types de mesophase. L'une de ces phases possede un reseau bidimensionnel hexagonal, l'autre un reseau bidimensionnel oblique

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Phasmids : a new class of liquid crystals

Nematic disc-like liquid crystals

An homologous series of hexa alkoxybenzoates of triphenylene has been prepared with n = 4 to n = 12. Interphase transitions between solid, mesomorphic and isotropic phases were studied by hot stage microscopy and differential scanning calorimetry. Binary phase diagram studies, optical textures observations and X-ray measurements showed the existence of three different mesomorphic phases: a nematic disc-like phase N D, a tilted columnar phase D t and a rectangular disordered columnar phase D rd. Only two different phases were observed in each compound and the following mesophase sequences were found. This remarkable even-odd effect is discussed and is compared to that observed for classic liquid crystals. Several hexa alkybenzoates of triphenylene (n = C7 − C10) were also prepared and their mesomorphic properties studied. Only short range N D were observed.

Nguyen Huu Tinh

Papers

Disc-Like Mesogen Polymorphism

Disc-Like Mesogens: A Classification

Phasmids : a new class of liquid crystals

Nematic disc-like liquid crystals

An Homologous Series of Disc-Like Mesogens with Nematic and Columnar Polymorphism