Asymmetrically Substituted Benzene‐1,3,5‐tricarboxamides: Self‐Assembly and Odd–Even Effects in the Solid State and in Dilute Solution

Molecular organization : Chiral benzene tricarboxamides with methyl substituents at defined positions self‐assemble into supramolecular polymers of preferred helicity by three‐fold α‐helical‐type hydrogen bonding. The odd–even effect is operative and all derivatives are liquid crystalline showing a Col_ho phase (see figure).

     

Synthesis and Chain‐Length Dependence of the Electronic Properties of π‐Conjugated Dithieno[3,2‐b:2′,3′‐d]pyrrole (DTP) Oligomers

N‐(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]pyrrole has been prepared and its dimer and trimer have been synthesized by Stille coupling. The electrochemical and optical properties of these compounds have been investigated by cyclic voltammetry, UV–Vis, and fluorescence emission spectroscopies. The obtained results show that these strongly luminescent compounds can be oxidized into stable cation radical and dication state. The analysis of the chain length dependence of the electronic properties indicates that the predicted bandgap of an ideal polymer chain should be considerably smaller than the experimental results reported until now. This difference is discussed in terms of reactivity of the dithieno[3,2‐b:2′,3′‐d]pyrrole (DTP) unit.

     

Electrochemical polymerization of imidazolum‐ionic liquids bearing a pyrrole moiety

A series of imidazolium‐based ionic liquid monomers bearing a terminal pyrrole moiety were synthesized and electrochemically polymerized. It is found that the polymerizability of the synthesized ionic liquids is strongly dependent on the type of the counteranions. Although bromide monomer is not polymerizable, well‐defined polymeric films can be formed on various substrates in the cases of flour‐containing anions (BF₄^?, PF₆^?). The performed characterizations show that all resulting polypyrrole films are electroactive, and the imidazolium‐based ionic liquid moieties are correctly incorporated in polymer films during the electropolymerization process. This work not only provides a facile new method to immobilize ionic liquids on solid surface. Interestingly, without use of any template unique “knit” morphology and nanostructure, even hierarchical structures could also be produced by the electropolymerization of these new functionalized pyrrole monomers. We found that the properties of the pendant ionic liquid units on the surface of the formed polymer films preserved, and by simple anion exchange their surface energy and tension could be easily tuned without loss of the electrical, optical properties, and morphology of the polypyrrole films. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4151–4161, 2008     

Robust Ordered Bundles of Porous Helical Nanotubes Assembled from Fully Rigid Ionic Benzene‐1,3,5‐tricarboxamides

Size‐controlled and ordered assemblies of artificial nanotubes are promising for practical applications; however, the supramolecular assembly of such systems remains challenging. A novel strategy is proposed that can be used to reinforce intermolecular noncovalent interactions to construct hierarchical supramolecular structures with fixed sizes and long‐range ordering by introducing ionic terminals and fully rigid arms into benzene‐1,3,5‐tricarboxamide (BTA) molecules. A series of similar BTA molecules with distinct terminal groups and arm lengths are synthesized; all form hexagonal bundles of helical rosette nanotubes spontaneously in water. Despite differences in molecular packing, the dimensions and bundling of the supramolecular nanotubes show almost identical concentration dependence for all molecules. The similarities of the hierarchical assemblies, which tolerate certain molecular irregularities, can extend to properties such as the void ratio of the nanotubular wall. This is a rational strategy that can be used to achieve supramolecular nanotubes in aqueous environments with precise size and ordering at the same time as allowing molecular modifications for functionality.     

DNA binding to electropolymerized N‐substituted polypyrrole surfaces

This study explores the use of N‐substituted polypyrroles as a route for localizing DNA molecules onto conducting surfaces. N‐substituted pyrrole monomers containing N‐hydroxysuccinimidyl groups for DNA binding reactions were synthesized. These monomers were electro‐copolymerized under different conditions on platinum or gold working electrodes in a three‐electrode/single compartment cell. Subsequent DNA reactions were performed by incubating the resulting polymer conductive films with amino‐substituted DNA sequences. In addition, the electro‐copolymerization reactions of pyrrole monomers were conducted on preselected electrode positions of the Molecular Nanosystems (MNS) wafers and the formation of conductive films was demonstrated. In these experiments, it was determined also that by controlling the electro‐copolymerization reactions, the conductive films can be restricted to grow on specific locations of the MNS wafer. This was achieved by electrically passivating the chosen electrodes with self‐assembled multilayers (SAM)s of alkane thiols. Hexadecane thiol (HDT) was found the most efficient in forming SAMs and in preventing the pyrrole electropolymerization. Various analytical techniques including AFM, IR, and cyclic voltammetry (CV) were used to characterize the monomers, the electropolymerized polymers, and the attachment of amine‐terminated DNA to polypyrrole copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6014–6024, 2009     

2-(对烷氧基苯甲酸酯基或对烷氧基苯丙烯酸酯基)-5-氧-2,5-二氢呋喃化合物的合成与液晶性质研究

Two series of p-alkoxybenzoates Ia-If and p-alkoxycinnamates IIa-IIf, each species beating one terminal furanone, have been synthesized and characterized by IR, ^13C NMR, ^1H NMR, MS spectra and elemental analysis. The mesogenic properties of both series of furanones have been studied by polarizing optical microscopy and differential scanning calorimetry （DSC）. The relationship between structures and mesogenic properties was discussed. The results show that the increased alkoxy chain length （C7-C12） and the bridging groups between the benzene ring and the furanone ring affected the mesomorphic properties greatly, and the two series of furanones might display monotropic or enantiotropic nematic （N） or semetic C （SmC） mesophases and different mesomorpic phase temperature ranges corresponding to different carbon chain length.     

Macroscopic Chirality of Supramolecular Gels Formed from Achiral Tris(ethyl cinnamate) Benzene‐1,3,5‐tricarboxamides

A C₃‐symmetric benzene‐1,3,5‐tricarboxamide substituted with ethyl cinnamate was found to self‐assemble into supramolecular gels with macroscopic chirality in a DMF/H₂O mixture. The achiral compound simultaneously formed left‐ and right‐handed twists in an unequal number, thus resulting in the macroscopic chirality of the gels without any chiral additives. Furthermore, ester–amide exchange reactions with chiral amines enabled the control of both the handedness of the twists and the macroscopic chirality of the gels, depending on the structures of the chiral amines. These results provide new prospects for understanding and regulating symmetry breaking in assemblies of supramolecular gels formed from achiral molecular building blocks.     

Liquid crystal alignment property of n‐alkylthiomethyl‐ or n‐alkylsulfonylmethyl‐substituted polystyrenes

We synthesized a series of n‐alkylthiomethyl‐substituted polystyrenes (#T‐PS, # = 4, 8, 12, and 16) and n‐alkylsulfonylmethyl‐substituted polystyrenes (#S‐PS, # = 4, 8, 12, and 16), where # is the number of carbon atoms in the n‐alkyl side group of the polymers, using polymer analogous reactions to investigate their liquid crystal (LC) alignment properties. In general, the LC cell fabricated using the polymer film having a longer n‐alkyl side group, a thioether linkage group, and a higher molar content of n‐alkyl side group showed homeotropic LC alignment behavior with a pretilt angle of about 90°. The homeotropic alignment behavior was well correlated with the surface energy of the polymer films; when the positive dielectric anisotropic LC (ZLI‐5900‐000 from Merck) and negative dielectric anisotropic LC (MLC‐7026‐000 from Merck) were used to fabricate the LC cells, homeotropic alignment was observed when the surface energy values of the polymer were smaller than about 25 and 32 mJ/m², respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Hydrogen bonding in polyamino‐polyalcohols: a monohydrated cocrystal of 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol iodide and 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol

In the title monohydrated cocrystal, namely 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol iodide–1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol–water (1/1/1), C₆H₁₆N₃O₃⁺·I⁻·C₆H₁₅N₃O₃·H₂O, the neutral 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci) molecule and the monoprotonated 1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol cation (Htaci⁺) both adopt a chair conformation, with the three O atoms in axial and the three N atoms in equatorial positions. The cation, but not the neutral taci unit, exhibits intramolecular O—H...O hydrogen bonding. The entire structure is stabilized by a complex three‐dimensional network of intermolecular hydrogen bonds. The neutral taci entities and the Htaci⁺ cations are each aligned into chains along [001]. In these chains, two O—H...N interactions generate a ten‐membered ring as the predominant structural motif. The rings consist of vicinal 2‐amino‐1‐hydroxyethylene units of neighbouring molecules, which are paired via centres of inversion. The chains are interconnected into undulating layers parallel to the ac plane, and the layers are further held together by O—H...N hydrogen bonds and additional interactions with the iodide counter‐anions and solvent water molecules.     

Crystal structure and morphologies of polypropylene homopolymer and propylene‐ethylene random copolymer: Effect of the substituted 1,3,5‐benzenetrisamides

Four different substituted 1,3,5‐benzenetrisamides were synthesized and two of them were reported for the first time. Their effects on the crystal structure and morphologies of the iPP homopolymer (PPH) and propylene‐ethylene random copolymers (PPR) were investigated. The results showed that they had versatile nucleating ability among the different crystal forms of PPH. The N,N′,N′′‐tris‐tert‐butyl‐1,3,5‐benzene‐tricarboxamide, N,N′,N′′‐tris‐cyclohexyl‐1,3,5‐benzene‐tricarboxamide, and N,N′,N′′‐tris‐isopropyl‐1,3,5‐benzene‐tricarboxamide suppressed the formation of detectable spherulites with the common α‐form of the PPH, as well as the N,N′,N′′‐n‐butyl‐1,3,5‐benzene‐tricarboxamide induced the spherulites of the β‐form. The combination of the ethylene segment and the nucleating agent facilitated the formation of the γ‐form. These trisamides had limited effects on the packing of the PPH segments but induced more compacted packing of the PPRs. The nucleation mechanism of such compounds was discussed for the first time, it was found that the nucleation ability of these compounds rooted in matching of their dimension of the b‐axis with dimension of the c‐axis of iPP, and their butterfly‐shape further enhanced it. The (001) face of the trisamides was in contact with the (010) face of iPP. This epitaxial crystallization led to preferential growth along the b‐axis, and the ethylene segment indeed enhanced this effect. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1067–1078, 2008     

Main chain 1,1′‐ferrocene‐containing polyelectrolytes exhibiting thermotropic liquid‐crystalline and fluorescent properties

A series of 1,1′‐ferrocene‐containing polyelectrolytes ( 3, 4 ) were prepared when 1,1′‐bis(N,N‐dimethylaminomethyl)ferrocene ( 1a ) or 1, 1′‐bis{[1‐(2‐methyl)imidazol‐1‐yl]methyl}ferrocene ( 1b ) was quaternized with 1,4‐dibromobutane or α, α′‐dibromo‐p‐xylene. The counterion was bromide or bis(trifluoromethanesulfonyl)‐amide formed after metathesis with the lithium salt. Their chemical structures were determined by IR and NMR spectra. Molecular weights in the range of ～5400 ( 4a )– ～14,700 ( 4c ) for number‐average molecular weights (M_n) over narrow molecular weight distributions were determined for polymers 4 by gel permeation chromatography. Thermal properties of these materials were obtained by differential scanning calorimetry and thermogravimetric analysis that showed the polymers had thermal stabilities ranging between 172 and 330 °C. Liquid‐crystalline behavior was investigated on a hot stage polarizing optical microscope. Polymers 3a , 4b , and 4d formed either a high‐order or a low‐order smectic phase above their melting or fusion temperatures, and exhibited smectic‐to‐isotropic transitions. The ranges of the liquid‐crystalline phases for these materials were 22, 46, and >55 °C. Compounds 3b , 4a , and 4c are crystalline before melting or decomposing. All of the polymers exhibited absorption bands at ～430 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 974–983, 2005     

Synthesis and characterization of poly (indene‐co‐pyrrole) nanofibers

Nanofibers of poly (indene‐co‐pyrrole) (CInPy) have been synthesized, using a facile chemical oxidative polymerization reaction. The effect of copolymerization was examined in view of the individually synthesized homopolymer nanostructures of polyindene (PIn) and polypyrrole (PPy). Morphological details of CInPy, studied using scanning electron microscopy (SEM) and transmission electron microscopy, (TEM) reveal the appearance of dense cottony mess, comprising of fine fibers with an average diameter of 5–10 nm. Chemical structural analysis of CInPy, conducted using ultraviolet‐visible (UV‐Vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR) spectroscopic techniques, reveals that both PIn and PPy are involved in the formation of copolymer organization. Fluorescence properties of nanosized copolymer are observed in the blue region, with emission λ_max placed at 395 nm. Conductivity of copolymer nanofibers (2.4 × 10^?3 S/cm) is consistent with the morphology and thermal stability properties of integral homo‐polymers. Improved thermal stability and processability along with the enhanced optical and electrical properties of copolymer nanostructures outfit it as a better promising material in optoelectronic and light emitting nanodevices, with reference to nanosized PIn and PPy. Copyright © 2009 John Wiley & Sons, Ltd.     

Fast switching response and dielectric behaviour of fullerene/ferroelectric liquid crystal nanocolloids

The electro-optical and dielectric responses of the fullerenes C₆₀-doped ferroelectric liquid crystal (FLC) nanocolloids are reported. Order parameter and phase transition temperature remain invariant as a function of varying dopant concentration (0.10 wt% to 0.50 wt%). Faster switching response of nanocolloids comparing to that of the non-doped FLC is manifested by increase in the localised electric field (around 76% increment for 0.50 wt%), while reduction in the spontaneous polarisation could be the result of anti-parallel correlation amid dopant and FLC dipoles. Decrease in dielectric constant, absorption strength, dielectric strength and rotational viscosity of FLC nanocolloids than that of non-doped FLC is the other consequence of C₆₀ doping. Goldstone-mode relaxation frequency is found to be increased with increasing doping concentration of C₆₀ in FLC.     

Synthesis and Supramolecular Assemblies of Tripodal 1,3,5‐Tris(phenoxymethyl)‐2,4,6‐triethylbenzene Analogues

Tripodal 1,3,5‐tris(phenoxymethyl)‐2,4,6‐triethylbenzene analogues have been synthesized and structurally characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and HRMS, and additionally, the single crystal structures of compounds bearing ortho‐ ( 7 ), meta‐ ( 9 ) and para‐hydroxymethyl ( 11 ) functions have been determined by X‐ray diffraction analysis. The structural study revealed that compounds 7 , 9 , and 11 do not adopt the expected 1,3,5‐alternate conformation in the solid state. The packing diagrams of compounds 7 , 9 , and 11 revealed that six hydrophilic hydroxymethyl groups from six individual molecules ( 7 , 9 and 11 ) were arranged in close contact via intermolecular hydrogen‐bond interactions. For compounds 7 and 9 , the six hydroxyl groups formed a distorted hexagonal ring; however, formation of such a hexagonal ring was not clear in the case of compound 11 . Compounds 9 and 11 were found to form hydrophobic cavities via intermolecular hydrogen‐bond interactions in the solid state, and the cavities were occupied by two ethyl groups from the two cavity‐forming molecules.     

Three different fluoro‐ or chloro‐substituted 1′‐deoxy‐1′‐phenyl‐β‐D‐ribofuranoses

Crystal structures are reported for three fluoro‐ or chloro‐substituted 1′‐deoxy‐1′‐phenyl‐β‐D‐ribofuranoses, namely 1′‐deoxy‐1′‐(2,4,5‐trifluorophenyl)‐β‐D‐ribofuranose, C₁₁H₁₁F₃O₄, (I), 1′‐deoxy‐1′‐(2,4,6‐trifluorophenyl)‐β‐D‐ribofuranose, C₁₁H₁₁F₃O₄, (II), and 1′‐(4‐chlorophenyl)‐1′‐deoxy‐β‐D‐ribofuranose, C₁₁H₁₃ClO₄, (III). The five‐membered furanose ring of the three compounds has a conformation between a C2′‐endo,C3′‐exo twist and a C2′‐endo envelope. The ribofuranose groups of (I) and (III) are connected by intermolecular O—H...O hydrogen bonds to six symmetry‐related molecules to form double layers, while the ribofuranose group of (II) is connected by O—H...O hydrogen bonds to four symmetry‐related molecules to form single layers. The O...O contact distance of the O—H...O hydrogen bonds ranges from 2.7172 (15) to 2.8895 (19) Å. Neighbouring double layers of (I) are connected by a very weak intermolecular C—F...π contact. The layers of (II) are connected by one C—H...O and two C—H...F contacts, while the double layers of (III) are connected by a C—H...Cl contact. The conformations of the molecules are compared with those of seven related molecules. The orientation of the benzene ring is coplanar with the H—C1′ bond or bisecting the H—C1′—C2′ angle, or intermediate between these positions. The orientation of the benzene ring is independent of the substitution pattern of the ring and depends mainly on crystal‐packing effects.     

Side‐chain liquid crystalline polyacrylates containing 3,4‐disubstituted pyrrole moiety

Polymerization of liquid crystalline bifunctional monomer N‐{{ω‐{4‐[4‐(11‐acryloyloxy)undecanoxybenzoyl]biphenyleneoxy} alkyl}}‐3,4‐dimethylpyrrole gave a side‐chain liquid crystalline polyacrylate containing 3,4‐dimethylpyrrole group. Liquid crystallinity was determined by DSC and optical polarizing microscope measurements. The monomers having pentylene, hexylene, and decylene as the alkylene spacer group between the mesogenic unit and the 3,4‐dimethylpyrrole group exhibited smectic and nematic phases on the heating and cooling stages. The radically polymerized polyacrylate derivatives containing the 3,4‐dimethylpyrrole group showed nematic phases on the heating and cooling stages. These polymers are the first example of side‐chain liquid crystalline polymers containing 3,4‐dimethylpyrrole as functional group for further reaction. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1214–1221, 2000     

A Simple Method for the Preparation of TiO2/Ag‐AgCl@Polypyrrole Composite and Its Enhanced Visible‐Light Photocatalytic Activity

A novel and facile method was developed to prepare a visible‐light driven TiO₂/Ag‐AgCl@polypyrrole (PPy) photocatalyst with Ag‐AgCl nanoparticles supported on TiO₂ nanofibers and covered by a thin PPy shell. During the synthesis, the PPy shell and Ag‐AgCl nanoparticles were prepared simultaneously onto TiO₂ nanofibers, which simplified the preparation procedure. In addition, because Ag‐AgCl aggregates were fabricated via partly etching the Ag nanoparticles, their size was well controlled at the nanoscale, which was beneficial for improvement of the contact surface area. Compared with reference photocatalysts, the TiO₂/Ag‐AgCl@PPy composite exhibited an enhanced photodegradation activity towards rhodamine B under visible‐light irradiation. The superior photocatalytic property originated from synergistic effects between TiO₂ nanofibers, Ag‐AgCl nanoparticles and the PPy shell. Furthermore, the TiO₂/Ag‐AgCl@PPy composite could be easily separated and recycled without obvious reduction in activity.     

Formation of lithium,sodium and potassium complexes with 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci)

Single crystals of (1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate, [Li(C₆H₁₆N₃O₃)(C₆H₁₅N₃O₃)]I₂·2H₂O or [Li(Htaci)(taci)]I₂·2H₂O (taci is 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol), (I), bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)sodium(I) iodide, [Na(C₆H₁₅N₃O₃)₂]I or [Na(taci)₂]I, (II), and bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)potassium(I) iodide, [K(C₆H₁₅N₃O₃)₂]I or [K(taci)₂]I, (III), were grown by diffusion of MeOH into aqueous solutions of the complexes. The structures of the Na and K complexes are isotypic. In all three complexes, the taci ligands adopt a chair conformation with axial hydroxy groups, and the metal cations exhibit exclusive O‐atom coordination. The six O atoms of the resulting MO₆ unit define a centrosymmetric trigonal antiprism with approximate D_3d symmetry. The interligand O...O distances increase significantly in the order Li < Na < K. The structure of (I) exhibits a complex three‐dimensional network of R—NH₂—H...NH₂—R, R—O—H...NH₂—R and R—O—H...O(H)—H...NH₂—R hydrogen bonds. The structures of the Na and K complexes consist of a stack of layers, in which each taci ligand is bonded to three neighbours via pairwise O—H...NH₂ interactions between vicinal HO—CH—CH—NH₂ groups.     

Dynamic Supramolecular Polymers Based on Benzene‐1,3,5‐tricarboxamides: The Influence of Amide Connectivity on Aggregate Stability and Amplification of Chirality

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 Col_ho. 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 (C?O)‐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 C?O‐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 Ph? NH bond compared to the Ph? CO 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 C?O BTAs.