Orientational control of guest molecules in an organic intercalation system by host polymer tacticity

Four kinds of stereoregular poly(muconic acid)s, which are synthesized by topochemical polymerization and subsequent solid-state hydrolysis, are used as the organic host materials for intercalation. We describe the reaction behavior and layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as IR and Raman spectroscopies. We have found that the orientation of the guest molecules is controlled by the host polymer tacticity, depending on the structure of the two-dimensional hydrogen-bonding network formed in the polymer sheets of the crystals.     

Fluorescence from aromatic compounds isolated in the solid state by double intercalation using layered polymer crystals as the host solid

Poly(muconic acid)s, stereoregular polymer crystals obtained by topochemical polymerization using supramolecular control, function as the layered host solids for organic intercalation, in which alkylamines as the guest species are reversibly inserted into them through an acid-base interaction. We now report a double-intercalation method using alkylamine and pyrene as the guests to control the fluorescence property in the solid state. An aromatic compound can be separately introduced into the hydrophobic layers of the ammonium polymer crystals. The aromatic molecules, which are sandwiched between two alkyl layers, show fluorescence emission from the single molecule but not the excimer. This method can be applied to various organic photofunctional materials showing unique fluorescence properties.     

Topochemical Polymerization of 1,3‐Diene Monomers and Features of Polymer Crystals as Organic Intercalation Materials

From the viewpoint of controlled polymer synthesis, topochemical polymerization based on crystal engineering is very useful for controlling not only the primary chain structures but also the higher‐order structures of the crystalline polymers. We found a new type of topochemical polymerization of muconic and sorbic acid derivatives to give stereoregular and high‐molecular weight polymers under photo‐, X‐ray, and γ‐ray irradiation of the monomer crystals. In this article, we describe detailed features and the mechanism of the topochemical polymerization of diethyl‐(Z,Z)‐muconate as well as of various alkylammonium derivatives of muconic and sorbic acids, which are 1,3‐diene mono‐ and dicarboxylic acid derivatives, to control the stereochemical structures of the polymers. The polymerization reactivity of these monomers in the crystalline state and the stereochemical structure of the polymers produced are discussed based on the concept of crystal engineering, which is a useful method to design and control the reactivity, structure, and properties of organic solids. The reactivity of the topochemical polymerization is determined by the monomer crystal structure, i.e. the monomer molecular arrangement in the crystals. Polymer crystals derived from topochemical polymerization have a high potential as new organic crystalline materials for various applications. Organic intercalation using the polymer crystals prepared from alkylammonium muconates and sorbates is also described.     

高分子-无机夹层化合物的合成、结构和性能

由高分子和插入无机层状固体层间形成的夹层化合物是近年发展起来的一类具有诱人前景的新型功能材料,在许多领域具有广的前景。本文对这夹层化合的合成、结构、性能及应用前景等方面的研究进展进行了评述。     

Solid-state hosts by the template polymerization of columnar liquid crystals: locked supramolecular architectures around chiral 2-amino alcohols

The cross-linking of multicomponent liquid crystals could be applied to the synthesis of nanometer-sized porous materials with a well-defined structure. In this work we demonstrate the template polymerization of columnar liquid crystals composed of the salts of a carboxylic acid and enantiopure 2-amino alcohols, and the application of one of them as a solid-state host. The salts of 3,4,5-tris(11-acryloyloxyundecyloxy)benzoic acid with (S)-2-amino-1-propanol and with (1R,2S)-norephedrine showed hexagonal and rectangular columnar liquid-crystalline structures, respectively. The successful application of gamma-ray-induced polymerization to the cross-linking of the liquid-crystalline salts, which was more advantageous than photoinduced polymerization from the standpoint of the retention of the original structural order in the gram-scale preparation of the polymers with a homogeneous columnar structure. The cross-linked polymer thus obtained from the gallic acid derivative and (1R,2S)-norephedrine was applicable as a heterogeneous host to capture amines from a guest solution through acid-amine interactions. When (1R,2S)-norephedrine was replaced with other amines through the guest-exchange reaction, a "template effect" was observed; the size and shape of the guests were determining factors for the efficiency of the guest exchange. The guest adsorption was found to proceed in an enantioselective manner when racemic 2-amino alcohols were used as guests, especially in the cases of substrates possessing a bulky substituent at the C1-position. The guest preference was again elucidated by the template effect, although the enantioselection mode was switched depending on the presence of a C2 substituent.     

Deintercalation of a chemically switchable polymer from a layered silicate nanocomposite

The phenomenon of intercalation is widely known as a key process in the area of polymer/layered silicate nanocomposites. In the formation of such nanocomposites, a polymer chain is intercalated between the layers of a layered (silicate) host, typically giving a well-ordered multilayered stack with a repeat distance of only a few nanometers. Intercalated systems are excellent models for studies of confined geometries, and they often display enhanced material properties as well. In this study, we examined a series of polymers in which it was possible to reverse the intercalation process (i.e., to achieve deintercalation). Homopolymers and copolymers of poly(methyl methacrylate) and poly(tetrahydropyranyl methacrylate) (PTHPMA) were intercalated into an organically modified synthetic fluoromica. Thermally induced deprotection of the tetrahydropyranyl group resulted in the transformation of PTHPMA into poly(methacrylic acid), which was then observed to deintercalate from the silicate host. X-ray diffraction and thermogravimetric analysis were used to study the deintercalation process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3151–3159, 2003     

First example of the topochemical polymerization of the (E,E)‐muconic acid derivative

The 1‐naphthylmethylammonium salts of not only (Z,Z)‐ but also (E,E)‐muconic acid were found to polymerize upon photoirradiation in the crystalline state to provide a stereoregular polymer in a high yield. The stereochemical structure of both polymers obtained from the monomers with different configurations was identical, i. e., a meso‐diisotactic‐trans‐2,5‐structure. The stereochemistry of the polymers obtained is discussed on the basis of the monomer configuration and the molecular packing in the crystals.     

Crystal engineering for topochemical polymerization of muconic esters using halogen-halogen and CH/pi interactions as weak intermolecular interactions

We now report the molecular and crystal structure design of muconic ester derivatives on the basis of crystal engineering using halogen-halogen contacts and CH/pi interactions. The solid-state photoreaction pathway of the dibenzyl (Z,Z)-muconates as the 1,3-diene dicarboxylic acid monomers depends on the structure of the ester groups. The substitution of a halogen atom for the aromatic hydrogen of a benzyl group induces topochemical polymerization to produce stereoregular polymers in a crystalline form, whereas the unsubstituted benzyl derivative isomerizes to yield the corresponding E,E isomer under similar conditions. The topochemical polymerization process is directly confirmed by the fact that the single-crystal structures before and after the polymerization are very similar to each other. From the crystal structure analysis for a series of substituted benzyl (Z,Z)- and (E,E)-muconates, it has been revealed that the planar diene moieties are closely packed to form a columnar structure in the crystals. The stacking of the polymerizable monomers is characterized by a stacking distance of 4.9-5.2 A along the columns. This structure is supported by a halogen-halogen interaction between the chlorine or bromine atoms introduced at the p position of the benzyl groups in addition to an aromatic stacking due to the CH/pi interaction between the benzylic methylene hydrogens and aromatic rings. The design of a monomer packing corresponds to the type and position of the introduced halogen atom and also the polymorphs. To make a stacking distance of 5 A using both halogen-halogen and CH/pi interactions as supramolecular synthons is important for the molecular design of muconic ester derivatives appropriate for topochemical polymerization.     

Organic intercalation material: reversible change in interlayer distances by guest release and insertion in sandwich-type inclusion crystals of cholic acid

Cholic acid (CA) forms inclusion crystals that have a sandwich-type lamellar structure constructed by the alternative stacking of host bilayers and guest layers. Five disubstituted benzenes, o-toluidine, m-fluoroaniline, o-chlorotoluene, o-bromotoluene, and indene, are accommodated in the two-dimensional void space between the host bilayers at 1:2 host-guest stoichiometries. Thermal gravimetric analysis of the inclusion crystals revealed that all the guest molecules, except o-toluidine, are released in two separate steps, indicating the formation of intermediate crystals after the first guest release. Adequate heat treatment of the four inclusion crystals induces release of half or three quarters of the guest molecules. X-ray diffraction patterns of the intermediate crystals revealed that the crystals have a bilayer structure the same as those of the common CA inclusion crystals. They have one-dimensional cavities, in which the guest molecules are included at a 1:1 or 2:1 host-guest stoichiometry. These facts indicate that the host bilayers move 1.6-4.5 A perpendicular to the layer direction by desorption of the guest molecules. Furthermore, a reverse structural change is also achieved by absorption of the guest molecules to regenerate the starting sandwich-type inclusion crystals. This reversible change in the host bilayer by the guest sorption and desorption is a novel example of organic intercalation materials.     

Self-assembly of polymer and molybdenum oxide into lamellar hybrid materials

We report on self-assembly of polymer and molybdenum oxide chains into a new class of lamellar hybrid materials. Aqueous ammonium molybdate and polyvinyl alcohol (PVA) or carboxymethyl cellulose (CMC) were used as the starting materials. Ammonium molybdate was hydrolyzed into layered molybdenum oxide under acidified conditions. The organic polymer chains and the inorganic molybdenum oxide layers self-assemble and pack into new hybrid composites. Scanning electron microscope (SEM) images and polarized microscopy show that these two new materials have typical lamellar structure. Transmission electron microscope (TEM) images show that the layer thickness is about 100 nm. X-ray diffraction (XRD) data confirm the formation of inorganic molybdenum oxide. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) data gave thermal behavior of these composites. The mechanism of this hybrid reaction and the templating function of polymers were discussed in this paper. A special entropy effect was discovered when polymer was used as guest species. This entropy effect makes polymers preferential candidates as guest species rather than small molecules when fabricating organic/inorganic layered hybrid materials. We believe that this opens a new way to create organic/inorganic hybrid superstructures.     

Application of mean-field model of polymer melt intercalation in organo-silicates for nanocomposites

The mean-field, lattice-based model of polymer melt intercalation in organically-modified layered silicates (OLS) originally developed by Vaia and Giannelis was applied for different polymers such as poly(methyl methacrylate) (PMMA), polypropylene (PP), and poly(ethylene oxide) (PEO). The nature of each polymer controls significantly the intercalation of the system. The internal energy change caused by the interaction of polymer, surfactant and clay is the strongest factor in determining the equilibrium structure of the nanocomposite system.     

Solid state polymerization of butadienes. Polymerization of long chain derivatives of sorbic and muconic acid

The polymerization of long chain derivatives of sorbic and muconic acid was studied in the solid state. Crystals of sorbic acid n-octadecylester (1), sorbic acid n-octadecylamide (2), and 6-n-octadecanoylamino sorbic acid (3) were found to rapidly polymerize upon UV- or-irradiation. A 1,4-trans-polymer was obtained in a high yield. Crystals of muconic acid di-n-octadecylester (4) and muconic acid di-n-octadecylamide (5) were completely photoinactive.Polymerization of3 was also investigated in monomolecular layers at the air-water interface and in Langmuir-blodgett type multilayers. The polymer formed upon UV- irradiation of mono- and multilayers was identified by infrared spectroscopy as the 1,4-trans-adduct.     

Intercalation of non-aromatic heterocyclic amines into layered zirconium glycine-<Emphasis Type="Italic">N,N</Emphasis>-dimethylphosphonate

New materials were prepared by intercalation reactions between layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) and non-aromatic heterocyclic amines: piperazine, piperidine, and morpholine. X-ray powder diffraction patterns showed that the entrance of piperazine, piperidine, and morpholine caused an interlayer expansion of 0.40 nm, 0.66 nm, and 0.67 nm, respectively. The infrared spectra were in agreement with an acid-base reaction, involving layered acid host COOH of ZGDMP and basic center atoms of guest molecules. Thermogravimetric curves revealed thermal stability of the intercalation compounds and content of the inserted amine molecules. These results indicate that non-aromatic heterocyclic amines were intercalated into the galleries of host ZGDMP.     

Supramolecular solids as a medium for single-crystal-to-single-crystal E/Z photoisomerization: kinetic study of the photoreactions of two Zn-coordinated tiglic acid molecules

[Zn(TA)2(H2O)2] (H-TA=tiglic acid) has been embedded in a framework composed of CECR (CECR=C-ethylcalix[4]resorcinarene) molecules to examine its E-->Z photoisomerization in a periodic framework. The photoisomerization of tiglic acid in CECR-[Zn(TA)2(H2O)2]4 H2O proceeds without the [2+2]-dimerization reaction that often occurs in crystals of uncomplexed analogues, and without breakdown of the crystal lattice that frequently occurs in neat crystals. The two Zn-coordinated TA molecules are located in different size cavities. The rate constants of the isomerization reaction are strongly affected by the size of the reaction cavity. Analysis of the temperature dependence of the reaction rates and the occupancies in the final photostationary state shows that the activation energies and the standard enthalpies of activation are dependent on the difference between the reaction cavities. This is the first quantitative diffraction study of solid-state E/Z isomerization of a metal-coordinated ligand in a periodic host environment.     

Amplified Chirality Transfer to Aromatic Molecules through Non-specific Inclusion by Amorphous,Hyperbranched Poly(fluorenevinylene) Derivatives

Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10⁻².     

Electronic structure of highly doped conducting polymers

Three-dimensional energy-band calculations on highly doped donor and acceptor compounds of polyacetylenes have been carried out using experimentally suggested channel and intercalation models for the structure of these conducting polymers. The band structures can be very well approximated by the superposition of bands calculated for the polymer chains without the presence of dopants and the bands calculated for the guest chains or layers, strongly supporting the rigid-band model (RBM ) for these structures. The absence of strong mixing between the guest and host orbitals explains the small perpendicular to the chain band widths (and corresponding resonance integrals as well) supporting interchain hopping models for the charge transport in these systems. The results are compared with calculations on graphite intercalation compounds (C₈K and C₇Br).     

三氧化钼/苯胺层状复合材料的制备

以三氧化钼为无机主体, 用十二烷基胺对三氧化钼层间进行改性, 成功地制备了三氧化钼/苯胺层状复合材料. X射线衍射、元素分析、扫描电子显微镜、红外光谱测试及差热分析结果表明, 苯胺分子已成功地插入三氧化钼层间, 所得复合物化学式为[ANI]0.4MoO3. 插层后, 三氧化钼仍保持规则有序的层状结构, 其层间距扩大至1.318 nm. 讨论了无机主体与有机客体之间的相互作用、苯胺在层间的可能排布形式以及苯胺插入层间的反应机理.     

Switching of structural order in a cross-linked polymer triggered by the desorption/adsorption of guest molecules

A cross-linked polymer, prepared by the in situ polymerization of a thermotropic columnar liquid crystal, was found to work as a host with a flexible framework, which was reminiscent of intercalation hosts, such as clays, graphites, and coordination polymers. The structural order of the cross-linked polymer was reversibly switched by changing the amount or shape of a guest incorporated in the polymer.     

High-density chemical intercalation of zero-valent copper into Bi2Se3 nanoribbons

A major goal of intercalation chemistry is to intercalate high densities of guest species without disrupting the host lattice. Many intercalant concentrations, however, are limited by the charge of the guest species. Here we have developed a general solution-based chemical method for intercalating extraordinarily high densities of zero-valent copper metal into layered Bi(2)Se(3) nanoribbons. Up to 60 atom % copper (Cu(7.5)Bi(2)Se(3)) can be intercalated with no disruption to the host lattice using a solution disproportionation redox reaction.     

Synthesis of ammonium substituted β-cyclodextrins for enantioseparation of anionic analytes

New ammonium functionalized cyclodextrins can be prepared in excellent yields by displacement of 6-tosyl-β-cyclodextrin with alkylimidazoles, pyridine or alkylamines and achieve excellent enantioseparation of dansyl amino acids presumably due to electrostatic interactions between the cationic host and anionic guest.