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Liquid Crystalline (liquid + crystalline)
Terms modified by Liquid Crystalline Selected AbstractsNature of water molecules in hydrogels based on a liquid crystalline cellulose derivativePOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 11-12 2003P. Wojciechowski Abstract The status and nature of water molecules in hydrogels with a liquid crystalline organization of the polymer network based on a biopolymer were investigated. Liquid crystalline (LC) hydrogels were obtained in situ by the photopolymerization of acrylic acid into the lyotropic liquid crystalline phase of (2-hydroxypropyl)cellulose in a solvent mixture of water and acrylic acid. The photopolymerization of acrylic acid in the lyotropic liquid crystalline phase at room temperature gives a hydrogel in which liquid crystalline order and water are retained. The liquid crystalline hydrogel contains water, which originates from the composition of the lyotropic liquid crystalline phase, and may also contain water after immersion in liquid water. The water molecule characteristics were examined by means of differential scanning calorimetry, dielectric relaxation spectroscopy, and differential scanning calorimetry coupled with thermo-optical measurements. The swelling data were obtained by using a weighing method. The investigations reveal the different nature of the two above-mentioned water types. For the water from the composition of the lyotropic liquid crystalline phase, the phase transitions,typical for the bulk water,were not observed, in contract to the water after swelling of the liquid crystalline hydrogel in the liquid water. The results of the measurements suggest that water, which comes from the composition of the lyotropic liquid crystalline phase, forms,together with a polymer network,a microstructure, stabilized by this water. The water, after swelling of the LC hydrogel in the liquid water, is separated in the pores of the hydrogel and exhibits the phase transitions of the bulk water. Copyright © 2003 John Wiley & Sons, Ltd. [source] Phase transition behavior and structure of the thermotropic liquid crystal 6-{[(4,-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyneCRYSTAL RESEARCH AND TECHNOLOGY, Issue 9 2006Leijing Liu Abstract The phase transition behaviors and corresponding structures of 6-{[(4,-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X-ray diffraction (WAXD). In comparison with the published homologues, 5-{[(4,-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5-{[(4,-heptoxy-biphenyl-4-yl)oxy]carbonyl}- 1-pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5-{[(4,-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5°C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69Å. Further lowering the temperature, it enters into a metastable monotropic smectic B (SmB) phase with a longer layer spacing d=34.22Å which has a tendency towards crystallization. The metastability of the liquid crystalline phase may associate to the linkage order of the ester bridge between the mesogenic core and the flexible spacer. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Photoswitchable Gas Permeation Membranes Based on Liquid CrystalsADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Eric G, owacki Abstract We have fabricated switchable gas permeation membranes in which a photoswitchable low-molecular-weight liquid crystalline (LC) material acts as the active element. Liquid crystal mixtures are doped with mesogenic azo dyes and infused into commercially available track-etched membranes with regular cylindrical pores (0.40 to 10.0 ,m). Tunability of mass transfer can be achieved through a combination of (1) LC/mesogenic dye composition, (2) surface-induced alignment, and (3) reversible photoinduced LC-isotropic transitions. Photo-induced isothermal phase changes in the imbibed material afford large and fully reversible changes in the permeability of the membrane to nitrogen. Both the LC and photogenerated isotropic states demonstrate a linear permeability/pressure relationship, but they show significant differences in their permeability coefficients. Liquid crystal compositions can be chosen such that the LC phase is more permeable than the isotropic,or vice versa , and can be further tuned by surface alignment. Permeability switching response times are 5 s, with alternating UV and >420-nm radiation at an intensity of 2 mW/cm2 being sufficient for complete and reversible switching. Thermal and kinetic properties of the confined LC materials are evaluated and correlated with the observed permeation properties. We demonstrate for the first time reversible permeation control of a membrane with light irradiation. [source] Biophysical characterization of synthetic rhamnolipidsFEBS JOURNAL, Issue 22 2006Jörg Howe Synthetic rhamnolipids, derived from a natural diacylated glycolipid, RL-2,214, produced by Burkholderia (Pseudomonas) plantarii, were analyzed biophysically. Changes in the chemical structures comprised variations in the length, the stereochemistry and numbers of the lipid chains, numbers of rhamnoses, and the occurrence of charged or neutral groups. As relevant biophysical parameters, the gel (,) to liquid crystalline (,) phase behavior of the acyl chains of the rhamnoses, their three-dimensional supramolecular aggregate structure, and the ability of the compounds to intercalate into phospholipid liposomes in the absence and presence of lipopolysaccharide-binding protein were monitored. Their biological activities were examined as the ability to induce cytokines in human mononuclear cells and to induce chemiluminescence in monocytes. Depending on the particular chemical structures, the physicochemical parameters as well as the biological test systems show large variations. This relates to the acyl chain fluidity, aggregate structure, and intercalation ability, as well as the bioactivity. Most importantly, the data extend our conformational concept of endotoxicity, based on the intercalation of naturally originating amphiphilic virulence factors into membranes from immune cells. This ,endotoxin conformation', produced by amphiphilic molecules with a hydrophilic charged backbone and apolar hydrophobic moiety, and adopting inverted cubic aggregate structures, causes high mechanical stress in target immune cells on integral proteins, eventually leading to cell activation. Furthermore, biologically inactive rhamnolipids with lamellar aggregate structures antagonize the endotoxin-induced activity in a way similar to lipid A-derived antagonists. [source] Liquid-Crystalline Polymer with a Block Mesogenic Side Group: Photoinduced Manipulation of Nanophase-Separated StructuresADVANCED FUNCTIONAL MATERIALS, Issue 23 2009Kunihiko Okano Abstract In this report, a novel type of photoresponsive liquid crystalline polymer with a block mesogenic side-group is demonstrated. The block mesogene is an amphipathic molecule containing a hydrophobic mesogene (azotolane moiety) and hydrophilic oligooxyethylene moieties in the same unit. The block mesogene in the polymer plays a role in liquid crystalline, amphiphilic and photoresponsive properties. As expected, a film prepared from the polymer exhibits phase separation of a lamellar structure due to cooperative motion between liquid crystal assembly and nanophase separation. The morphology of the lamellae can be aligned upon irradiation of linearly polarized light. Moreover, a photochemical phase transition induced by unpolarized UV irradiation erases the surface morphology. The erased nanostructure can be recovered by annealing or irradiation of linearly polarized light, meaning that the surface morphology is rewritable via a photochemical process. [source] Formation of Highly Luminescent Supramolecular Architectures Possessing Columnar Order from Octupolar Oxadiazole Derivatives: Hierarchical Self-Assembly from Nanospheres to Fibrous Gels,ADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Shinto Varghese Abstract The synthesis and study of the liquid crystalline, photophysical, and aggregation behavior of novel octupolar oxadiazole derivatives are reported. These molecules formed columnar mesophases at elevated temperatures which transformed into a glassy state at ambient temperatures wherein the columnar order was retained. Their spontaneous concentration dependent hierarchical self-assembly from spheres to fibrous gels has been investigated using TEM, SEM, and XRD. Retention of the hexagonal columnar (Colh) order was also observed in the fibrous aggregates. Concentration dependent luminescence spectral studies indicated that the change in morphology from spheres to fibrous aggregates was associated with a shift in chromophore packing from predominantly H -type to J -type aggregates. Time resolved anisotropic investigations revealed that the columnar stacking of molecules in the aggregated state provided a pathway for excitation energy migration to the lower energy J -traps. [source] Synthesis of liquid crystalline,amorphous block copolymers by the combination of atom transfer and promoted cationic polymerizationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007S. Demirhan Abstract Block copolymers of liquid crystalline 6-(4-cyanobiphenyl-4,-oxy) hexyl acrylate (LC6) and cyclohexene oxide (CHO) were obtained by the combination of atom transfer radical polymerization (ATRP) and promoted cationic polymerization (PCP). In the first part, a bifunctional initiator containing benzoin and halide groups in the same structure was used as an initiator in ATRP of LC6, in diphenyl ether in conjunction with CuBr/N,N,N,,N,,N,-pentamethyldiethylenetriamine as a catalyst. The obtained photoactive liquid crystalline polymers poly[6-(4-cyanobiphenyl-4,-oxy)hexyl acrylate] (PLC6), were used to induce polymerization of CHO through formation of electron donor polymeric radicals upon photolysis and subsequent oxidation to corresponding carbocations in the presence of onium salt. The spectral, thermal and optical measurements confirmed a full combination of ATRP and PCP, which resulted in the formation of AB-type block copolymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [source] Using terahertz pulsed spectroscopy to quantify pharmaceutical polymorphism and crystallinityJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 4 2005Clare J. Strachan Abstract Terahertz pulsed spectroscopy (TPS) is a new technique that is capable of eliciting rich information when investigating pharmaceutical materials. In solids, it probes long-range crystalline lattice vibrations and low energy torsion and hydrogen bonding vibrations. These properties make TPS potentially an ideal tool to investigate crystallinity and polymorphism. In this study four drugs with different solid-state properties were analyzed using TPS and levels of polymorphism and crystallinity were quantified. Carbamazepine and enalapril maleate polymorphs, amorphous, and crystalline indomethacin, and thermotropic liquid crystalline and crystalline fenoprofen calcium mixtures were quantified using partial least-squares analysis. Root-mean-squared errors of cross validation as low as 0.349% and limits of detection as low as approximately 1% were obtained, demonstrating that TPS is an analytical technique of potential in quantifying solid-state properties of pharmaceutical compounds. © 2005 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 94:837,846, 2005 [source] [5-(p -alkoxy)phenyl-10, 15, 20-tri-phenyl] porphyrin and their rare earth complex liquid crystallineJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 4 2007Miao Yu Abstract Three series of porphyrin liquid crystalline compounds, [5-(p -alkoxy)phenyl-10, 15, 20-tri-phenyl] porphyrin and their rare earth complexes (Tb (III), Dy (III), Er (III), Yb (III)), with a hexagonal columnar discotic columnar(Colh) phase have been synthesized. These compounds were characterized by elemental analysis, molar conductances, UV-visible spectra, infrared spectra, luminescence spectra, and cyclic voltammetry. These compounds exhibit more than one mesophases, which transition points of temperature change from ,33.6 to 16.0,°C, and transition points of temperature for isotropic liquid also increase from 4.9 to 38.2,°C, with increasing chain length. Their surface photovoltage (SPV) response have also been investigated by the means of surface photovoltage spectroscopy (SPS) and field-induced surface photovoltage spectroscopy (EFISPS). It was found that their SPV bands are analogous with the UV-visible absorption spectra and derived from the same transition. Copyright © 2007 John Wiley & Sons, Ltd. [source] Synthesis and hierarchical superstructures of side-chain liquid crystal polyacetylenes containing galactopyranoside end-groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2009Ming-Shou Ho Abstract Three kinds of chiral saccharide-containing liquid crystalline (LC) acetylenic monomers were prepared by click reaction between 2-azidoethyl-2,3,4,6-tetraacetyl-,- D -galactopyranoside and 1-biphenylacetylene 4-alkynyloxybenzoate. The obtained monomers were polymerized by WCl6 -Ph4Sn to form three side-chain LC polyacetylenes containing 1-[2-(2,3,4,6-tetraacetyl-,- D -galactopyranos-1-yl)-ethyl]-1H -[1,2,3]-triazol-4,-biphenyl 4-alkynyloxybenzoate side groups. All monomers and polymers show a chiral smectic A phase. Self-assembled hiearchical superstructures of the chiral saccharide-containing LCs and LCPs in solution state were studied by field-emission scanning electron microscopy. Because of the LC behavior, the LC molecules exhibit a high segregation strength for phase separation in dilute solution (THF/H2O = 1:9 v/v). The self-assembled morphology of LC monomers was dependent upon the alkynyloxy chain length. Increasing the alkynyloxy chain length caused the self-assembled morphology to change from a platelet-like texture (LC-6) to helical twists morphology (LC-11 and LC-12). Furthermore, the helical twist morphological structure can be aligned on the polyimide rubbed glass substrate to form two-dimensional ordered helical patterns. In contrast to LC monomers, the LCP-11 self-assembled into much more complicate morphologies, including nanospheres and helical nanofibers. These nanofibers are evolved from the helical cables ornamented with entwining nanofibers upon natural evaporation of the solution in a mixture with a THF/methanol ratio of 3:7. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6596,6611, 2009 [source] Liquid crystalline conjugated polymers and their applications in organic electronicsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2009Sheng-Hsiung Yang Abstract This article describes the syntheses and electro-optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p -phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p -phenylenevinylene)s, the Suzuki- or Yamamoto-coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main-chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side-chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field-effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo-fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713,2733, 2009 [source] Synthesis and liquid crystalline properties of new amide-modified poly(1,4-cyclohexanedimethylene terephthalate),JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2006P. Deepa Abstract New series of cycloaliphatic poly(ester-amide)s, poly(1,4-cyclohexanedimethyleneterephthalate- co -1,3-cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4-cyclohexanedimethanol and 1,3-cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester-amides). The thermal analysis indicate that the new poly(ester-amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester-amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory,Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42,52, 2006 [source] UV-Curable Azobenzene Polymer Bearing Photo-Crosslinkable Moiety for Stabilization of Photo-Fabricated Surface Relief StructureMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 16 2002Tatsumi Kimura Abstract In order to find a new class of photo-processable liquid crystalline (LC) aligning material, five kinds of new maleimide-based copolymers bearing both azobenzene and cinnamate moieties with different functionalization ratio have been synthesized. The properties of these five copolymers were compared regarding physical and chemical properties that are required for our aim. The photo-induced surface relief (PSR) gratings could be fabricated on the films of these copolymers using an Ar+ laser (,,=,488 nm), and were successfully immobilized and bleached by UV-light irradiation that causes photo-crosslinking of the cinnamate moiety and photo-degradation of the azobenzene moiety, respectively. The PSR inscription rate and the thermal stability have been investigated regarding the functionalization ratio between cinnamate and azobenzene side chain. The residual ratio of the PSR structure after UV-curing was increased with increasing photo-crosslinkable moiety. It was confirmed that the UV-cured PSR grating structure becomes transparent at visible wavelength and was able to align LC molecules parallel to the grating direction. Polarized optical microscope image of LC cell aligned by the PMPDC 21-18 film with UV-cured PSR structure (0°). [source] Orientation and Dynamics of ZnO Nanorod Liquid Crystals in Electric FieldsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 12 2010Matthias Zorn Abstract ZnO nanorod polymer hybrids (i.e., ZnO nanorods coated with a block copolymer with a short anchor block (dopamine) and a longer solubilizing block of polystyrene (PS)) form liquid crystalline (LC) phases if they are dispersed at high concentration e.g., in a PS oligomer matrix. Due to the high mobility of the low Tg -matrix the nanorod polymer hybrids show a switching behavior under an applied AC electric field. Hence, the orientation of the nanorod mesogens can be changed from planar (parallel to the substrate) to homeotropic (perpendicular) in full analogy to the switching of low molecular liquid crystals in an electric field. Dielectric measurements show that such a switching is mainly due to the cooperative LC behavior, because the rods themselves exhibit only a very small effective dipole moment. The process can be investigated by polarizing microscopy. SEM images show the orientations of the individual nanorods, which correspond to the Fredericks transition well known for liquid crystals aligned in an electric field. This was the first time such a transition could be visualized by electron microscopy due to the large nanorod mesogens. The observation is interesting to orient nanorods perpendicular to an electrode and can help to improve optoelectronic devices. [source] Structural characterization of poly(diethylsiloxane) in the crystalline, liquid crystalline and isotropic phases by solid-state 17O NMR spectroscopy and ab initio MO calculationsMAGNETIC RESONANCE IN CHEMISTRY, Issue 3 2005Hideaki Kimura Abstract The structure of poly(diethylsiloxane) (PDES) has been characterized using solid-state NMR of 17O. The sample studied had a weight-average molecular weight of 2.45 × 105. The sample was prepared by utilizing the cationic ring-opening polymerization of 17O-enriched hexacyclotrisiloxane. Solid-state NMR of 17O-enriched PDES was measured on the low-temperature ,1 phase, the high-temperature ,2 phase, the two-phase system consisting of the liquid crystal and isotropic liquid phase and the isotropic phase. From these data, the molecular structure and dynamics of PDES in the various phases were characterized via the chemical shifts of 17O, and electric field gradient parameters were determined from NMR and ab initio molecular orbital (MO) calculations. In addition to the solid-state NMR of 1H, 13C and 29Si previously reported on these samples, knowledge of the dynamic behavior of PDES as inferred from the NMR of 17O in the present study was enhanced significantly. Further, the potential of combining the experimental NMR of 17O with ab initio MO calculations to characterize the dynamics of polymers containing oxygen is demonstrated. Copyright © 2004 John Wiley & Sons, Ltd. [source] Synthesis and characterization of liquid crystalline elastomers bearing fluorinated mesogenic units and crosslinking mesogensPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 12 2009Fan-Bao Meng Abstract Several new side-chain liquid crystalline (LC) polysiloxanes and elastomers (IP - VIP) bearing fluorinated mesogenic units and crosslinking mesogens were synthesized by a one-step hydrosilylation reaction with poly(methylhydrogeno)siloxane, a fluorine-containing LC monomer 4,-undec-10-enoyloxy-biphenyl-4-yl 4-fluoro-benzoate and a crosslinking LC monomer 4,-(4-allyloxy-benzoxy)-biphenyl-4-yl 4-allyloxy-benzoate. The chemical structures and LC properties of the monomers and polymers were characterized by use of various experimental techniques such as FTIR, 1H-NMR, EA, TGA, DSC, POM and XRD. The effect of crosslinking mesogens on mesomorphic properties of the fluorinated LC polymers was studied as well. The obtained polymers and elastomers were soluble in many solvents such as toluene, tetrahydrofuran, chloroform, and so forth. The temperatures at which 5% weight loss occurred (Td) were greater than 250°C for all the polymers, and the weight of residue near 600°C increased slightly with increase of the crosslinking mesogens in the fluorinated polymer systems. The samples IP, IIP, IIIP and IVP showed both smectic A and nematic phases when they were heated and cooled, but VP and VIP exhibited only a nematic mesophase. The glass transition temperature (Tg) of polymers increased slightly with increase of crosslinking mesogens in the polymer systems, but the mesophase,isotropic phase transition temperature (Ti) and smectic A,nematic mesophase transition temperature (TS-N) decreased slightly. It suggests that the temperature range of the mesophase became narrow with the increase of crosslinking mesogens for all the fluorinated polymers and elastomers. In XRD curves, the intensity of sharp reflections at low angle decreased with increase of crosslinking mesogens in the fluorinated polymers systems, indicating that the smectic order derived from fluorinated mesogenic units should be destroyed by introduction of more crosslinking mesogens. Copyright © 2008 John Wiley & Sons, Ltd. [source] Dynamic Supramolecular Polymers Based on Benzene-1,3,5-tricarboxamides: The Influence of Amide Connectivity on Aggregate Stability and Amplification of ChiralityCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2010Patrick Abstract N-Centred benzene-1,3,5-tricarboxamides (N-BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid-state behaviour and self-assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X-ray diffraction revealed that the chiral N-BTA derivatives with branched 3,7-dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Colho. In contrast, N-BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable-temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N-BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N-BTAs revealed a cooperative self-assembly behaviour of the N-BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants-and-soldiers as well as the majority-rules principles were operative in stacks of N-BTAs. In fact, the self-assembly of N-BTAs resembles closely that of their carbonyl (CO)-centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self-assembly of N- and CO-BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N-BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the PhNH bond compared to the PhCO bond and the diminished magnitude of dipole,dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N-BTAs and CO BTAs. [source] Star Mesogens (Hekates),Tailor-Made Molecules for Programming Supramolecular FunctionalityCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2009Matthias Lehmann Abstract Hekates: Modular synthesis of star-shaped molecules affords mesogens with various functional units and incompatible peripheral chains (see figure). The supramolecular order in the complex, soft, liquid-crystalline, functional materials can be programmed by variation of the elements of diversity at a meso- and nanoscale. This concept article focuses on the simplest branched liquid crystalline (LC) molecules,the three-armed mesogens with arms symmetrically linked to the core. They are basic but fascinating mesogens for the exploration of self-assembling processes into complex, functional, soft materials. Quite a large number of elements of diversity provide the possibility to synthetically program such star-shaped molecules and to control phase formation, if aggregation processes are fully understood. Recently, ABC-cores opened the way to non-symmetric mesogens and, therefore, to the concept of multifunctional materials with defined nanostructures. In the article this outstanding family of mesogens is classified, their peculiar molecular structure and self-assembly are discussed and potential applications are presented, in which this type of mesogen may be beneficial. Dieser Konzeptbeitrag stellt die einfachsten verzweigten flüssigkristallinen Moleküle in den Mittelpunkt,dreiarmige Mesogene mit symmetrisch um einen Kern angeordneten Armen. Diese schlichten, aber faszinierenden Mesogene eignen sich hervorragend für das Studium von Selbstorganisationsprozessen zu komplexen, funktionalen, weichen Materialien. Die große Zahl von Diversitätselementen, der modular aufgebauten Mesogene, ermöglicht das synthetische Programmieren der sternförmigen Moleküle und die Kontrolle der Anordnung in LC Phasen, falls die Aggregationsprozesse völlig verstanden werden. Die kürzlich vorgestellten ABC-Kerne erlauben die Synthese von unsymmetrischen Mesogenen und folglich die Umsetzung des Konzepts der multifunktionalen Materialien mit definierten Nanostrukturen. In diesem Artikel wird diese außergewöhnliche Mesogenfamilie klassifiziert und deren besondere Struktur und Selbstorganisation diskutiert. Schließlich werden mögliche Anwendungen vorgestellt, für die diese Art der Mesogene vorteilhaft sein kann. [source] Tuning the Polarization Along Linear Polyaromatic Strands for Rationally Inducing Mesomorphism in Lanthanide Nitrate ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 6 2007Emmanuel Terazzi Dr. Abstract The opposite orientation of the ester spacers in the rodlike ligands L,4C12 (benzimidazole-OOC-phenyl) and L,5C12 (benzimidazole-COO-phenyl) drastically changes the electronic structure of the aromatic systems, without affecting their meridional tricoordination to trivalent lanthanides, LnIII, and their thermotropic liquid crystalline (i.e., mesomorphic) behaviors. However, the rich mesomorphism exhibited by the complexes [Ln(L,4C12)(NO3)3] (Ln=La,Lu) vanishes in [Ln(L,5C12)(NO3)3], despite superimposable molecular structures and comparable photophysical properties. Density functional theory (DFT) and time-dependant DFT calculations performed in the gas phase show that the inversion of the ester spacers has considerable effects on the electronic structure and polarization of the aromatic groups along the strands, which control residual intermolecular interactions responsible for the formation of thermotropic liquid-crystalline phases. As a rule of thumb, an alternation of electron-poor and electron-rich aromatic rings favors intermolecular interactions between the rigid cores and consequently mesomorphism, a situation encountered for L,4C12, L,5C12, [Ln(L,4C12)(NO3)3], but not for [Ln(L,5C12)(NO3)3]. The intercalation of an additional electron-rich diphenol ring on going from [Ln(L,5C12)(NO3)3] to [Ln(L,6C12)(NO3)3] restores mesomorphism despite an unfavorable orientation of the ester spacers, in agreement with our simple predictive model. [source] Effect of Core Twisting on Self-Assembly and Optical Properties of Perylene Bisimide Dyes in Solution and Columnar Liquid Crystalline PhasesCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2007Zhijian Chen Abstract A series of highly soluble and fluorescent core-twisted perylene bisimide dyes (PBIs) 3,a,f with different substituents at the bay area (1,6,7,12 positions of the perylene core) were synthesized and fully characterized by 1H,NMR, UV/Vis spectroscopy, MS spectrometry, and elemental analysis. The ,,, aggregation properties of these new functional dyes were investigated in detail both in solution and in condensed phase by UV/Vis and fluorescence spectroscopy, vapor pressure osmometry (VPO), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. Concentration-dependent UV/Vis measurements and VPO analysis revealed that these core-twisted ,-conjugated systems show distinct self-dimerization equilibria in apolar solvent methylcyclohexane (MCH) with dimerization constants between 1.3×104 and 30,M,1. The photoluminescence spectra of the dimers of PBIs 3,a,f exhibit bathochromic shifts of quite different magnitude which could be attributed to different longitudinal or rotational offsets between the dyes as well as differences in the respective ,,, stacking distance. In condensed state, quite a few of these PBIs form luminescent rectangular or hexagonal columnar liquid crystalline phases with low isotropization temperatures. The effects of the distortion of the , systems on their ,,, stacking and the optical properties of the resultant stacks in solution and in LC phases have been explored in detail. In one case (3,a) a particularly interesting phase change from crystalline into liquid crystalline could be observed upon annealing that was accompanied by a transformation from non-fluorescent H -type into strongly fluorescent J -type packing of the dyes. [source] | |||||||||||||