Polymeric complexes of silver(I) with diphosphine ligands: self-assembly of a puckered sheet network structure

The syntheses and structures of polymeric silver(I)-diphosphine complexes are reported, in which the silver(I) center is surrounded by 1, 2, or 3 phosphorus atoms. When rigid diphosphine ligands are used in combination with weakly coordinating anions, linear polymers are obtained that contain both diphosphine and anion bridges. However, with excess of a diphosphine with a long, flexible, spacer group, a remarkable puckered sheet structure, comprised of fused giant 54-membered rings, is obtained that is a coordination polymer analogue of laminated materials such as micas and clays. The polymeric chain and sheet structures may be considered to be formed by ring-opening polymerization of cyclic precursors.     

Fabrication of conjugated polymeric nanochannels from star-shaped supramolecular liquid crystals containing two different photoreactive groups

New conjugated polymeric nanochannels were prepared via photopolymerisation and core extraction of star-shaped supramolecular liquid crystals formed by simple hydrogen bonding between a phloroglucinol core and pyridine derivatives containing two different photoreactive groups. The polymerisable supramolecular liquid crystal exhibited a discotic columnar mesophase. Photopolymerisation of supramolecular liquid crystalline monomer provided cross-linked conjugated polymeric columns in which the diacetylene and acrylate moieties were selectively polymerised along the vertical and horizontal axes, respectively. Chemical treatment of the cross-linked conjugated columns with sodium hydroxide resulted in the removal of the phloroglucinol core to produce the cross-linked conjugated polymeric nanochannels with an estimated effective pore diameter of about 1 nm. The controlled methodology in the present study can be used to design and fabricate conjugated nanoporous organic materials with intriguing ordered structures.     

Supramolecular side chain liquid crystalline polymers assembled via hydrogen bonding between carboxylic acid-containing polysiloxane and azobenzene derivatives

Supramolecular side chain liquid crystalline polymers were prepared from poly(3-carboxypropylmethylsiloxane) (PSI100) and azobenzene derivatives through intermolecular hydrogen bonding (H-bonding) between the carboxylic acid groups in the PSI100 and the imidazole rings in the azobenzene derivatives. The existence of H-bonding has been confirmed using FTIR spectroscopy. The polymeric complexes behave as liquid crystalline (LC) polymers and exhibit stable mesophases. The LC behaviour of these H-bonded polymeric complexes was investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The complexes exhibit nematic LC phases identified on the basis of Schlieren optical textures. On increasing spacer length or the concentration of the H-bonded mesogenic unit in the complex, the clearing temperature and the temperature range of the LC phase of the polymeric complex increase. The terminal group plays a critical role in determining the LC properties of the polymeric complexes. A terminal methoxy group is more efficient than a nitro group in increasing the clearing temperature. The electron donor-acceptor interactions between the H-bonded mesogenic units containing methoxy and nitro terminal groups in supramolecular 'copolymeric' complexes lead to an increase in the clearing temperature and a wider temperature range for the LC phase.     

Supramolecular side chain liquid crystalline polymers assembled via hydrogen bonding between carboxylic acid-containing polysiloxane and azobenzene derivatives

Supramolecular side chain liquid crystalline polymers were prepared from poly(3-carboxypropylmethylsiloxane) (PSI100) and azobenzene derivatives through intermolecular hydrogen bonding (H-bonding) between the carboxylic acid groups in the PSI100 and the imidazole rings in the azobenzene derivatives. The existence of H-bonding has been confirmed using FTIR spectroscopy. The polymeric complexes behave as liquid crystalline (LC) polymers and exhibit stable mesophases. The LC behaviour of these H-bonded polymeric complexes was investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The complexes exhibit nematic LC phases identified on the basis of Schlieren optical textures. On increasing spacer length or the concentration of the H-bonded mesogenic unit in the complex, the clearing temperature and the temperature range of the LC phase of the polymeric complex increase. The terminal group plays a critical role in determining the LC properties of the polymeric complexes. A terminal methoxy group is more efficient than a nitro group in increasing the clearing temperature. The electron donor-acceptor interactions between the H-bonded mesogenic units containing methoxy and nitro terminal groups in supramolecular 'copolymeric' complexes lead to an increase in the clearing temperature and a wider temperature range for the LC phase.     

Development of Poly(Phenylene)-Based Materials for Thin Film Applications: Optical Waveguides and Low Dielectric Materials

Abstract

We have synthesized and evaluated poly(phenylene)-based materials made via spin-coatable polymeric precursors for such thin film applications as optical waveguides and low dielectric materials. Poly(phenylene) precursors were prepared by radical polymerization of cyclohexadiene-1, 2-diol derivatives containing various leaving groups. The precursors were converted into poly(phenylene) either by curing at 300°C or by deep-UV exposure in the presence of a photoacid generator. Poly(phenylene) has a number of desirable properties including good near-IR transmission, low dielectric constant, thermal and environmental stability, low water absorption, and ease of pattern fabrication using microlithographic techniques. Copolymer precursors based on 1,2-diaceto-3,5-cyclohexadiene and styrene derivatives as well as copolymers with Nsubstituted maleimide derivatives were prepared by radical copolymerization. The copolymer precursors were converted into poly(phenylene) copolymers either by annealing at 300°C or by deep-UV exposure in the presence of a photoacid generator. The results of this study indicate that copolymerization allows the incorporation of comonomers that can control dielectric and optical properties as well as glass transition temperature.     

Recognition-directed supramolecular assemblies of metal complexes of terpyridine derived ligands with self-complementary hydrogen bonding sites

The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but partially broken grid with a quarter of the H-bonding sites unsaturated (d(N-H-N)=2.984-3.206 A). In the case of the Zn complex 12 with triflate anions, half of the hydrogen bonds are formed. Only one of the two orthogonal ligands has hydrogen bonds (d(N-H-N) = 3.082, 3.096 A) to the neighbouring complexes and thus builds linear, supramolecular, polymeric chains. These structural differences are mainly attributed to crystal-packing effects caused by the different anions. The data presented here may also be regarded as a prototype for the generation of organised arrays through sequential self-assembly processes.     

Synthesis of Conjugated Optically Active Polymetallocenes

The development of methodology for synthesizing new materials in which metal atoms are linked by hydrocarbons whose electronic conjugation is unbroken is described. The fundamental idea is to twist the hydrocarbons into helices. By attaching bulky groups to their precursors, the helices can be made to twist mainly in one direction. The molecules synthesized are helicenes capped by five-membered rings to which metals are attached. If the size of the helix is chosen appropriately, a polymeric structure forms in which hydrocarbon rings and metal atoms alternate. An oligomer with Structure 22 is the first such material prepared. It and related structures might be precursors of molecular solenoids, examples of which are not yet known.     

Fabrication of Neutral Supramolecular Polymeric Films via Post‐electropolymerization of Discrete Metallacycles

Self‐assembly post‐modification has proven to be an efficient strategy to build higher‐order supramolecular architectures and functional materials. In this study, we successfully realized the construction of a new family of neutral supramolecular polymeric films containing well‐defined metallacycles as the main scaffolds through combination of coordination‐driven self‐assembly with post‐electropolymerization. The obtained neutral polymeric materials were fully characterized by the cyclic voltammogram (CV), SEM, and TEM. The thickness of the films was able to be well regulated by the number of scanning cycles. Moreover, we found that the shape of the metallacycles and the number of triphenylamine moieties played important roles in the formation of the final polymer films. We believe that the introduction of the neutral metallacycles into the final polymer structures not only enriches the library of supramolecular polymeric films but also provides a new platform to study neutral molecule detection, separation, and capture.     

Preparation and surface properties of low-density gels synthesized using prepolymerized silica precursors

Properties of silica xerogels and aerogels synthesized using a number of prepolymerized silica precursors were probed by 29Si magic-angle spinning (MAS) NMR spectroscopy, the small-angle X-ray scattering (SAXS) method, the nitrogen adsorption method, and transmission electron microscopy (TEM) to show that xerogels with attractive textural properties can easily be prepared using this type of precursors and the conventional one-step, base procedure. Pore sizes and overall pore volumes in these materials can be notably larger than those in the corresponding materials synthesized using tetraethoxysilane. This positive effect stems from the stronger structure of the polymeric network due to a higher degree of silica condensation on one side and a larger thickness of polymeric chains on the other. The thorough investigations of the fine silica structure demonstrate, however, that the relationship between the microstructure of the silica precursor and the micro- and macrostructures of dry gels is complex and the use of more condensed precursors favors, but does not necessarily ensure, more porous dry materials, under the same reaction conditions. Ethyl silicate 40 may be recommended as a low-cost precursor suitable for applications in this situation.     

TiO2-Based Porous Materials Obtained from Gels, in Different Experimental Conditions

The gels which are precursors of TiO₂ porous materials are prepared by the controlled hydrolysis-condensation of titanium isopropoxide by polymeric method. In the present work, a study of the influence of different experimental conditions (water/alkoxide ratio, solvent/alkoxide ratio and temperature) on the structure and texture of the polymeric gels obtained with the same type of alkoxide has been investigated. The structural and textural modifications for the unsupported materials have been detected using DTA/TGA, XRD, specific surface area and pore size computerized measurements. The optical properties of the supported materials deposited on silicon wafers have been investigated using ellipsometric method. Supported and unsupported porous materials with different structure and texture have been obtained depending on different experimental and thermal treatment conditions.     

Hydrolytically stable thermoplastic and thermosetting poly(arylene phosphine oxide) material systems

Several thermoplastic and thermosetting polymeric materials containing the phenyl phosphine oxide group were prepared and characterized by physical methods. High molecular weight poly(arylene ether)s and polyimides containing the hydrolytically stable bulky phosphine oxide unit were synthesized and found to be soluble materials with moderately high glass transition temperatures. The phenyl phosphine oxide moiety was further incorporated into epoxy and bismaleimide type crosslinked systems. Phosphorus promoted char formation in air was displayed by both the linear and crosslinked macromolecules, leading to improved self-extinguishability relative to the non-phosphorus containing analogous polymeric systems.     

In situ photopolymerization of biomaterials by thiol-yne click chemistry

The thiol-yne click chemistry reaction has been used for the in situ photocrosslinking of an aliphatic hyperbranched polyester. The biocompatibility of the resulting networks has been studied and marked cytotoxicity was not found for HeLa (human cervical carcinoma) tumoral cells and COS7 fibroblasts. The photoinduced thiol-yne process allows the generation of patterned structures with different geometries in films by DLW and these materials can be used as substrates for cell adhesion. The influence of the substrate geometry on cell adhesion has been studied by culturing cells onto these substrates and a preference for the photopatterned polymeric material can be seen in some of the structures by contrast phase microscopy. Actin and vinculin fluorescent staining revealed different adhesion behavior for HeLa cells and COS7 fibroblasts and this could be assigned to the different motility of cells. The thiol-yne photoreaction has proven to be an attractive approach for the preparation of micropatterned biomaterials.     

Aggregation behaviour of peptide-polymer conjugates containing linear peptide backbones and multiple polymer side chains prepared by nitroxide-mediated radical polymerization

A series of peptides with an alternating sequence of alkoxyamine conjugated lysine and glycine residues were synthesized by classical solution phase peptide coupling. The resulting peptides containing up to eight alkoxyamine moieties were used as initiators in nitroxide-mediated polymerization (NMP) to obtain peptide-polymer conjugates with well defined linear peptide backbones and a defined number of polymeric side chains. Polymerization of styrene and N-isopropylacrylamide (NIPAM) occurred in a highly controlled fashion. Molecular weight and polydispersity index (PDI) were determined by gel permeation chromatography (GPC). Aggregation behaviour of these hybrid materials was investigated by dynamic light scattering (DLS) and atomic force microscopy (AFM). Depending on composition, number and length of the polymer side chains, the conjugates aggregate to different topologies. Whereas peptide-polystyrene conjugates may aggregate to so called honeycomb structures, peptide-poly-N-isopropylacrylamide conjugates show differentiated aggregation behaviour.     

Impact of graphitic carbon nitrides synthesized from different precursors on Schottky junction characteristics

Graphitic carbon nitride (g-CN) has gained wide interest in many areas, such as energy and the environmental remediation as a layered polymeric semiconductor that allows the formation of catalytically active Schottky junctions due to its proper electronic band structure. Interestingly, although it is known that the precursors used in the synthesis, can influence the properties of the g-CN, no detailed study on these effects on Schottky junctions could be found in the literature. In this research, the effects of g-CNs synthesized by thermal polycondensation of different precursors on the photocatalytic efficiency of Schottky junctions were investigated. For this purpose, urea, thiourea, melamine, and guanidine hydrochloride were used as different precursors, while the photocatalytic dehydrogenation of formic acid was used as a test reaction. The Schottky junctions were formed by decorating the as-prepared g-CNs with AgPd alloy nanoparticles (NP), which were synthesized by reduction of Ag and Pd salts with NaBH₄. The structural, electronic and charge carrier dynamics of all prepared structures have been fully characterized by TEM, XRD, BET, XPS, UV-Vis DRS, PL, and PL life measurements. The results showed that the charge transfer dynamics of g-CNs surface defects are more effective in the photocatalytic performance of Schottky junctions than in structural features such as the size of the metal NPs or the surface area of the catalysts.     

Supramolecular liquid-crystalline materials: molecular self-assembly and self-organization through intermolecular hydrogen bonding

Supramolecular liquid-crystals are molecular complexes formed from different and independent molecular species through specific molecular interactions such as hydrogen bonding. We have recently developed new types of H-bonded liquid-crystalline materials obtained by molecular self-assembly processes: (1) doubly H-bonded liquid-crystalline complexes through a molecular recognition process between 2,6-bis(acylamino)pyridines and benzoic acids, (2) liquid-crystalline polymer blends involving an H-bonding interaction between poly(4-vinylphenol) and a thermotropic main-chain polyester containing a lateral pyridyl substituent, (3) liquid-crystalline networks built through hydrogen bonds between multifunctional H-bonding components. These new materials may bridge a gap between liquid crystals and supramolecular systems.     

Identification and quantification of (polymeric) hindered-amine light stabilizers in polymers using pyrolysis-gas chromatography-mass spectrometry and liquid chromatography-ultraviolet absorbance detection-evaporative light scattering detection

Direct analysis of polymers containing polymeric hindered amine light stabilizers (HALS) by using pyrolysis coupled to GC-MS is applied successfully for fast and straightforward identification of these HALS additives. Each of the HALS additives shows different pyrolysis gas chromatograms containing characteristic pyrolysis products. As a result, HALS additives with very similar chemical structures, e.g. Chimassorb 944 and Chimassorb 2020, can be distinguished. A HPLC method with both ultraviolet (UV) and evaporative light scattering detection (ELSD) is developed to quantify the various HALS additives in extracts of polymers. The critical factor of the HPLC method is the use of a basic amine, like n-hexylamine, as a solvent additive to facilitate the elution of HALS additives. The various HALS additives can be distinguished according to retention time and peak shape and by using different detection methods. The suitability of the developed methods is demonstrated by the analytical performance of the HPLC method and the identification and determination of the actual content of HALS additives in polyolefines using pyrolysis GC-MS and HPLC. The HPLC method can also be used for the determination of the specific migration of HALS additives from food contact materials.     

Mn2O3纳米结构的简易合成与电化学性质

用简易的室温或水热方法制备出不同形貌的MnCO₃微结构。经600 ℃热处理后,室温制备MnCO₃转变成Mn₂O₃胶体片,而水热制备MnCO₃样品则形成多孔Mn₂O₃纳米结构。然而,室温制备MnCO₃经120 ℃热处理后形成Mn₂O₃晶相。制备样品经过XRD和SEM表征表明,热处理MnCO₃前驱物形成Mn₂O₃过程导致产物形貌与结构变化。其形成机理又通过TEM和FTIR进一步研究。Mn₂O₃纳米结构的电容性质通过循环伏安法表征,结果表明Mn₂O₃形貌与结构对其电容有重要影响。     

CO2 in supramolecular chemistry: preparation of switchable supramolecular polymers

CO2 gas was used to construct novel types of supramolecular polymers. Self-assembling nanostructures 11 and 13 were prepared, which employ both hydrogen bonding and dynamic, thermally reversible carbamate bonds. As precursors, calixarene ureas 1 and 2 were synthesized, which strongly aggregate/dimerize (K(D)>/=10(6) M(-1) per capsule) in apolar solution with the formation of self-assembling capsules 7 and linear polymeric chains 8, respectively, and also possess "CO2-philic" primary amino groups on the periphery. CO2 effectively reacts with molecules 7 and 8 in apolar solvents and cross-links them with the formation of multiple carbamate salt bridges. Oligomeric aggregate 11 and three-dimensional polymeric network 13 were prepared and characterized by 1H and 13C NMR spectroscopy. The morphology of supramolecular gel 13 was studied by scanning electron microscopy. Addition of a competitive solvent destroyed the hydrogen bonding in assembling structures 11 and 13, but did not influence the carbamate linkers; carbamate salts 12 and 14, respectively, were obtained. On the other hand, thermal release of CO2 from 11 and 13 was easily accomplished (1 h, 100 degrees C) while retaining the hydrogen-bonding capsules. Thus, three-dimensional polymeric network 13 was transformed back to linear polymeric chain 8 without breaking up. Encapsulation and storage of solvent molecules by 11 and 13 was demonstrated. This opens the way for switchable materials, which reversibly trap, store, and then release guest molecules. A two-parameter switch and control over hydrogen bonding and CO2-amine adducts was established.     

Thermal stability and degradation kinetics of novel organic/inorganic epoxy hybrid containing nitrogen/silicon/phosphorus by sol-gel method

Hybrids containing silicon, phosphorous and nitrogen were prepared by the sol-gel method and compared with pure epoxy. The silicon, phosphorous and nitrogen components were successfully incorporated into the networks of polymer. Thermogravimetric analysis (TGA) was used for rapid evaluation of the thermal stability of different materials. The integral procedure decomposition temperature (IPDT) has been correlated the volatile parts of polymeric materials and used for estimating the inherent thermal stability of polymeric materials. The IPDT of pure epoxy was 464 °C and the IPDTs of hybrids were higher than that of pure epoxy. The thermal stability of hybrids increased with the contents of inorganic components. The inorganic components can improve the thermal stability of pure epoxy.Two methods have been used to study the degradation of hybrids containing silicon, phosphorous and nitrogen hybrid during thermal analysis. These investigated methods are Kissenger, Ozawa's methods. The activation energies (E_a) were obtained from these methods and compared. It is found that the values of E_a for modified epoxy hybrids are higher than that of pure epoxy. The hybrids of high activation energy possess high thermal stability.