Thermotropic columnar mesophases from N–H⋯O, and N⋯H–O hydrogen bond supramolecular mesogenes
TL;DR: In this paper, the structures of columnar mesophases that depend on the presence of either N-H⋯O, or H-O-Bonds (subsumed under the term ‘N|H|O-bonds') are reviewed.
Abstract: The structures of supramolecular columnar mesophases that depend on the presence of either N–H⋯O, or N⋯H–O– hydrogen bonds (subsumed under the term ‘N|H|O-bonds’) are reviewed. The thesis is supported that supramolecular mesogenes bridge different fields of liquid crystal research, offering the opportunity to create a unified picture of thermotropic, and lyotropic mesomorphism. With the examples of N|H|O hydrogen bond mesogenes the molecular structures of the respective mesogenes are presented, and general principles to rationally construct such molecules are discussed. A connection is drawn to systems from isolated columns as found in low molecular weight organogels. Perspectives, and outlooks for possible applications of N|H|O hydrogen bonded columnar phases are given.
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TL;DR: New approaches to the functionalization of liquid crystals are described and it is shown how the design ofliquid crystals formed by supramolecular assembly and nano-segregation leads to the formation of a variety of new self-organized functional materials.
Abstract: In the 21st century, soft materials will become more important as functional materials because of their dynamic nature. Although soft materials are not as highly durable as hard materials, such as metals, ceramics, and engineering plastics, they can respond well to stimuli and the environment. The introduction of order into soft materials induces new dynamic functions. Liquid crystals are ordered soft materials consisting of self-organized molecules and can potentially be used as new functional materials for electron, ion, or molecular transporting, sensory, catalytic, optical, and bio-active materials. For this functionalization, unconventional materials design is required. Herein, we describe new approaches to the functionalization of liquid crystals and show how the design of liquid crystals formed by supramolecular assembly and nano-segregation leads to the formation of a variety of new self-organized functional materials.
1,400 citations
TL;DR: This Review will focus on the major classes of columnar mesogens rather than presenting a library of columner liquid crystals, and emphasis will be given to efficient synthetic procedures, and relevant mesomorphic and physical properties.
Abstract: 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.
1,056 citations
TL;DR: New exciting soft-matter structures distinct from the usually observed nematic, smectic, and columnar phases are presented, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry-breaking.
Abstract: Since the discovery of the liquid-crystalline state of matter 125 years ago, this field has developed into a scientific area with many facets. This Review presents recent developments in the molecular design and self-assembly of liquid crystals. The focus is on new exciting soft-matter structures distinct from the usually observed nematic, smectic, and columnar phases. These new structures have enhanced complexity, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry-breaking. Comparisons are made with developments in related fields, such as self-assembled monolayers, multiblock copolymers, and nanoparticle arrays. Measures of structural complexity used herein are the size of the lattice, the number of distinct compartments, the dimensionality, and the logic depth of the resulting supramolecular structures.
456 citations
TL;DR: The synthesis, self-assembly, and gelation ability of a series of organogelators based on perylene bisimide (PBI) dyes containing amide groups at imide positions are reported, which points to a self-sorting process.
Abstract: The synthesis, self-assembly, and gelation ability of a series of organogelators based on perylene bisimide (PBI) dyes containing amide groups at imide positions are reported. The synergetic effect of intermolecular hydrogen bonding among the amide functionalities and pi-pi stacking between the PBI units directs the formation of the self-assembled structure in solution, which beyond a certain concentration results in gelation. Effects of different peripheral alkyl substituents on the self-assembly were studied by solvent- and temperature-dependent UV-visible and circular dichroism (CD) spectroscopy. PBI derivatives containing linear alkyl side chains in the periphery formed H-type pi stacks and red gels, whereas by introducing branched alkyl chains the formation of J-type pi stacks and green gels could be achieved. Sterically demanding substituents, in particular, the 2-ethylhexyl group completely suppressed the pi stacking. Coaggregation studies with H- and J-aggregating chromophores revealed the formation of solely H-type pi stacks containing both precursor molecules at a lower mole fraction of J-aggregating chromophore. Beyond a critical composition of the two chromophores, mixed H-aggregate and J-aggregate were formed simultaneously, which points to a self-sorting process. The versatility of the gelators is strongly dependent on the length and nature of the peripheral alkyl substituents. CD spectroscopic studies revealed a preferential helicity of the aggregates of PBI building blocks bearing chiral side chains. Even for achiral PBI derivatives, the utilization of chiral solvents such as (R)- or (S)-limonene was effective in preferential population of one-handed helical fibers. AFM studies revealed the formation of helical fibers from all the present PBI gelators, irrespective of the presence of chiral or achiral side chains. Furthermore, vortex flow was found to be effective in macroscopic orientation of the aggregates as evidenced from the origin of CD signals from aggregates of achiral PBI molecules.
396 citations
TL;DR: In this paper, the authors discuss the recent advances in control over various polymerization systems, including ionic, radical, coordination and even polycondensation have enabled synthesis of many new well-defined (co)polymers and some of them are briefly discussed.
Abstract: Macromolecular engineering includes: rational design of the macromolecular structure including chain size, uniformity, topology, microstructure (sequencing and tacticity), composition and functionality; precise synthesis with high selectivity at reasonable cost, both in effort and environmental impact; assembly of macromolecules to supramolecular objects via controlled processing, including temperature, pressure, solvents, mechanical stresses, etc.; detailed characterization of the prepared materials at both molecular and macroscopic level; modeling of polymerization and processing conditions to aid in the design of appropriate conditions to reach targeted properties and function, and optimization of the entire process. Some recent unprecedented advances in control over various polymerization systems, including ionic, radical, coordination and even polycondensation have enabled synthesis of many new well-defined (co)polymers and some of them are briefly discussed. Precise control of various aspects of macromolecular architecture, including topology, functionality and microstructure have been achieved both in homogeneous and heterogeneous polymerization system and applied to preparation of polymeric hybrids, conjugates and other functional materials. The well-defined (co)polymers self-assembly or can be pre-assembled to materials with precisely controlled morphologies which can be affected and fixed by processing. The final macroscopic materials properties depend on molecular structure of (co)polymers and can be rationally retro-designed.
364 citations
References
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TL;DR: In this paper, a simple theory is developed that accounts for many of the observed physical properties of micelles, both globular and rod-like, and of bilayer vesicles composed of ionic or zwitterionic amphiphiles.
Abstract: A simple theory is developed that accounts for many of the observed physical properties of micelles, both globular and rod-like, and of bilayer vesicles composed of ionic or zwitterionic amphiphiles. The main point of departure from previous theories lies in the recognition and elucidation of the role of geometric constraints in self-assembly. The linking together of thermodynamics, interaction free energies and geometry results in a general framework which permits extension to more complicated self-assembly problems.
4,563 citations
TL;DR: The ability to prepare structures in the upper part of this range of sizes would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.
Abstract: Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.
3,119 citations
2,798 citations
01 Dec 1991
TL;DR: In this article, self-assembly is defined as the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds.
Abstract: Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.
2,591 citations
TL;DR: In this article, the Maier-Saupe model with an orientational order parameter is extended to the smectic $A$ phase by introducing a new order parameter, the amplitude of a density wave in the direction of the nematic preferred axis.
Abstract: The Maier-Saupe model of the nematic phase with an orientational order parameter is extended to the smectic $A$ phase by introducing a new order parameter, the amplitude of a density wave in the direction of the nematic preferred axis. Self-consistent equations for the two order parameters are derived from an anisotropic model interaction and are solved numerically. We calculate the order parameters, the entropy, and the specific heat as a function of temperature for several values of dimensionless interaction strength $\ensuremath{\alpha}$ for the smectic $A$ phase. The transition temperatures plotted versus $\ensuremath{\alpha}$ provide a theoretical phase diagram which resembles experimental plots of transition temperature versus alkyl chain length for homologous series of compounds. The model qualitatively reproduces chemical trends in transition entropies. Experiments are suggested to measure the order parameters in the smectic $A$ phase.
873 citations