Metal-containing conjugated oligo- and polythiophenes

Conjugated polymers containing metal groups are an important class of new materials that may find application as sensors, non-linear optical materials and in molecular electronics. Polythiophenes are an extensively studied class of conjugated polymers, that can be easily modified synthetically, and may be prepared using a variety of methods. Metal groups pendant to polythiophene backbones modulate the electronic, optical and redox properties of the conjugated backbone and can introduce novel structural motifs to these materials. Functionalization of oligo- and polythiophenes by Fe, Pd and Ru containing groups is discussed, along with the properties of some of these materials.     

Correlating Molar Mass, π-Conjugation,and Optical Properties of Narrowly Distributed Anionic Polythiophenes in Aqueous Solutions

Polythiophene-based conjugated polyelectrolytes (CPE) are attracting increasing attention as sensor or interface materials in chemistry and biology. While cationic polythiophenes are better understood, limited structural information is available on their anionic counterparts. Limited access to well-defined polymers has made the study of structure-property relationships difficult and clear correlations have remained elusive. By combining controlled Kumada catalyst transfer polymerization with a polymer-analog substitution, regioregular and narrowly distributed poly(6-(thiophen-3-yl)hexane-1-sulfonate)s (PTHS) with tailored chain length are prepared. Analysis of their aqueous solution structures by small-angle neutron scattering (SANS) revealed a cylindrical conformation for all polymers tested, with a length close to the contour length of the polymer chains, while the estimated radii remain too small (<1.5 nm) for extensive π-stacking of the chains. The latter is particularly interesting as the longest polymer exhibits a concentration-independent structured absorption typical of crystalline polythiophenes. Increasing the ionic strength of the solution diminishes these features as the Coulomb repulsion between the charged repeat units is shielded, allowing the polymer to adopt a more coiled conformation. The extended π-conjugation, therefore, appears to be a key parameter for these unique optical features, which are not present in the corresponding cationic polythiophenes.     

Functionalized conducting polymers for chemical sensors – an in situ ESR/UV‐Vis‐NIR voltammetric study

The redox and optical properties of various well defined polymer and copolymer films containing pyrrole or thiophene units were studied. The in situ ESR/UV‐Vis‐NIR spectroelectrochemistry was applied to investigate polymers and copolymers deposited both electrochemically or by a special chemical procedure using adhesion promoter onto the optically transparent indium‐tin‐oxide (ITO) electrodes. The spectroelectrochemical responses of chemically and electrochemically prepared polythiophenes on ITO were compared and the electronic structures of both polymers found to be similar. In situ ESR/UV‐Vis‐NIR voltammetric studies on electrochemically prepared copolymers containing pyrrole units and various N,N′‐ethylene‐bis(salicylidenimine) (salen) transition metal complexes indicate the presence of both polysalen and polypyrrole redox active centers in the copolymer.     

圆偏振发光高分子的研究

综合评述了近年来有关圆偏振发光高分子的研究，包括圆偏振发光高分子的潜在应用及其在发光高分子理论研究上的意义，圆偏振发光高分子的类型与性能表征等。并提出了三条获得高度圆偏振发光高分子的可能途径。     

Bandgap Engineering through Controlled Oxidation of Polythiophenes

The use of Rozen’s reagent (HOF?CH₃CN) to convert polythiophenes to polymers containing thiophene‐1,1‐dioxide (TDO) is described. The oxidation of polythiophenes can be controlled with this potent, yet orthogonal reagent under mild conditions. The oxidation of poly(3‐alkylthiophenes) proceeds at room temperature in a matter of minutes, introducing up to 60 % TDO moieties in the polymer backbone. The resulting polymers have a markedly low‐lying lowest unoccupied molecular orbital (LUMO), consequently exhibiting a small bandgap. This approach demonstrates that modulating the backbone electronic structure of well‐defined polymers, rather than varying the monomers, is an efficient means of tuning the electronic properties of conjugated polymers.     

Preparation of iridescent-reflective poly(furan-co-phenylene)s by electrochemical polymerization in a cholesteric liquid crystal medium

Optically active poly(4,4′-di(2-furyl)biphenyl) is successfully prepared by asymmetric electrochemical polymerization in a cholesteric liquid crystal (CLC) electrolyte. The polymer thus obtained forms a fingerprint optical texture similar to that of the CLC electrolyte and a convexo-concave surface structure along the fingerprint pattern. The polymer displays iridescence under irradiation with white light, and circular diffraction upon laser irradiation.     

含三氰乙烯基强吸电子基团的环氧树脂基非线性光学聚合物的合成

非线性光学聚合物材料及其在聚合物电光调制器中的应用是目前国内外研究的前沿。环氧树脂类聚合物具有很好的成膜性及可化学交联性能,是一类非常好的非线性光学聚合物的基体材料。本论文从分子设计的角度出发,将含三氰乙烯基强吸电子取代基及噻吩芳杂环共轭结构非线性光学生色团成功引入环氧树脂类聚合物,并在生色团侧基上引入甲基取代基。结果表明,苯胺残基中侧位甲基取代基对于先驱聚合物的亲电取代反应程度及最后聚合物的紫外-可见光最大吸收波长均有一定的影响,对于没有侧甲基的BP-TA-TC和一个侧甲基取代基的BP-3-TA-TC其官能化度均可以达到80%以上,而对于含两个甲基取代的BP-3,5-TA-TC先驱聚合物其官能化度则相对较低(低于10%)。随着甲基取代数目的增多,最后非线性光学聚合物的最大吸收波长也有不同程度的蓝移。     

ELECTRONIC EFFECTS OF POLYFLUORINATED SUBSTITUENTS ON THE POLYMERIZATION AND THE PROPERTIES OF POLYTHIOPHENES

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the electrochemical polymerization of thiophene mono-mers and properties of the obtained polymers were analyzed. The introduction of a flu-oroether functional group at the 3-position of the thiophene ring leads to an increase ofthe oxidation potential of the monomer and to a decrease of the conductivity of the re-sulting polymers, even with the use of a CH_2 group as spacer. Conversely, the presenceof an oxygen atom directly at the 3-position of the thiophene ring, which offsets the nega-tive withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conductingpolythiophenes.     

Preparation and characterization of cyclodextrin polymer and its high-performance liquid-chromatography stationary phase.

Cyclodextrin (CD) polymers were synthesized from the reaction of native CDs with a hexamethylene diisocyanate (HDI) compound in a dried DMF solution. The obtained CD polymer contained a range of 8-14% N due to HDI by elemental analysis. The physical and chemical properties of the CD polymers were characterized by IR, solid state 13C NMR, TGA, and DSC, respectively. An HPLC column was prepared using the CD polymer with a carbamate linker by a slurry method. Separation of the phenol isomers was conducted using the CD polymer stationary phase and CD by HPLC. Furthermore, an inclusion complex of the phenol isomer was studied by FT-Raman spectroscopy. From the HPLC and FT-Raman results, inclusion phenomena of o-, m-, and p-nitrophenol onto CD and CD polymers were analyzed.     

Synthesis and characterization of a new acceptor (n‐type) fluorinated and terminal‐functionalized polythiophene

Donor‐ or acceptor‐substituted polythiophenes have many potential applications in optoelectronics. Fluorinated polythiophenes are particularly attractive because of the presence of fluorine, which can withdraw electrons and also improve polymer chemical stability. Because of the promising future of these polymers, there has been much interest in identifying favorable synthetic routes to new fluorinated monomers and polymers. In this study, the monomer had an electron‐withdrawing fluorinated ester and was derived from 3‐thiophene carboxylic acid and 2,2,3,3,4,4,4‐heptafluoro‐1‐butanol. The synthesis of an n‐type fluorinated and terminal‐functionalized polythiophene was accomplished with the Ullmann coupling reaction. A polymer soluble in tetrahydrofuran was obtained with a molecular weight of approximately 15,000 g/mol. In solution, it exhibited a band gap of 2.4 eV, and the photoluminescent excitation and emission maxima were 370 nm and 555 nm, respectively. All peaks were bathochromically shifted when they were measured in the solid state. The glass‐transition and decomposition (in air) temperatures were 129 and 493 °C, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4280–4287, 2005     

Formation of higher-order structures of chiral poly(ethynylpyridine)s depending on size, temperature, and saccharide recognition

Amphiphilic 2,6-pyridylene ethynylene "meta-ethynylpyridine" polymers having chiral oligo(oxyethylene) side chains were developed as hosts for saccharide recognition. The polymers were prepared via a Sonogashira reaction and fractionated by gel permeation chromatography (GPC). They showed circular dichroism (CD) activity due to their higher-order chiral helical structures, and their CD and UV-vis spectra changed depending on not only saccharide recognition but also molecular size, temperature, and metal cation recognition.     

STRUCTURAL ANALYSIS AND ENVIRONMENTAL STABILITY OF POLYFLUORINATED GROUP SUBSTITUTED POLYTHIOPHENES

Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes givespolymers with relatively high molecular weights and good processibility. Investigationof these polymers by means of GPC indicates that an increase in the number of fluorineatoms in the fluorinated group results in a decrease in degree of polymerization of thepolymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluo-rinated group substituted polythiophenes have regular 2, 5-coupling in their main chains.The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymersdo. Substitution of polythiophenes by fluorinated groups leads to the polymers with highelectric, electrochemical and thermal stability.     

Potentiometric response of poly(3-octylthiophene), poly(3-methylthiophene) and polythiophene in aqueous solutions

The potentiometric response of some polythiophenes in aqueous solutions has been investigated. Polythiophene (PT), poly(2,2'-bithiophene) (PBT), poly(3-methylthiophene) (PMT), poly(3-octylthiophene) (POT) and poly(4,4'-dioctyl2,2'-bithiophene) (POTd) were electrochemically deposited on platinum in 0.1M LiBF(4)-propylene carbonate solution containing the corresponding monomer or dimer. Polymer electrodes were also prepared by solution casting of chemically synthesized poly(3-octylthiophene) (POTc) dissolved in chloroform. After film deposition (electrochemical or chemical) the polymer coated electrodes were used as indicator electrodes in potentiometric measurements. The open-circuit potential of the polymer electrodes was measured in aqueous solutions containing inorganic salts (10(-1)-10(-4)M). Interestingly, all the polythiophenes studied were found to give a cationic response to monovalent cations such as H(+), Li(+), Na(+), K(+) and NH(+)(4) (Cl(-) salts). The slope, calculated from the linear part of the response curve, was found to depend on the polythiophene used but always remained lower than that predicted for a Nernstian response. The polythiophenes also showed some sensitivity to divalent cations such as Mg(2+) and Ca(2+) (Cl(-)-salts). POT was used as the polymer to study the influence of the polymerization conditions on the potentiometric response. By investigating different polymers from the polythiophene family it was possible to evaluate how the starting material (monomer or dimer) and the presence of alkyl side-chains influence the potentiometric response of the polymer membranes.     

Synthesis of Liquid Crystalline Polymers with Side Chains

The present paper covers the synthesis and characterization of several intermediate products, monomer, and polymers. 3-{ 2-[ 4-( 4-Nitrophenylazo ) phenoxy] ethyloxycarbonyl} propanoyloxy (2-hydroxy) propyl acrylate (4) was prepared by the ring-opening reaction of glycidyl acrylate with the monoester of succinic acid (3). The polymers (5) with different molecular weights were prepared by the free-radical polymerization. The polymers (5) had liquid crystalline behavior without decomposition as revealed by DSC, optical microscope.     

SYNTHESIS AND CHARACTERIZATION OF POLYMERS BEARINGAZOBENZENE AND CARBAZOLE GROUPS VIA POST-AZO-COUPLING REACTION

A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationchromatography.This approach is more facile compared with the direct polymerization of corresponding functionalmonomer.The polymers prepared have weight average molecular weight of higher than 1.5×10~4 and are easily soluble incommon organic solvents like chloroform and tetrahydrofuran,polymer films with high optical quality could be easilyfabricated through solution casting.Glass transition temperature (T_(?)) of the polymers ranges from 60℃to 182℃,dependingon the alkylene spacer length between the functional side group and the polymer backbone,and the polymers are relativelystable under 300℃.     

Conducting polyfurans by electropolymerization of oligofurans

Polyfurans have never been established as useful conjugated polymers, as previously they were considered to be inherently unstable and poorly conductive. Here, we show the preparation of stable and conducting polyfuran films by electropolymerization of a series of oligofurans of different chain lengths substituted with alkyl groups. The polyfuran films show good conductivity in the order of 1 S cm^–1, good environmental and electrochemical stabilities, very smooth morphologies (roughness 1–5 nm), long effective conjugation lengths, well-defined spectroelectrochemistry and electro-optical switching (in the Vis-NIR region), and have optical band-gaps in the range of 2.2–2.3 eV. A low oxidation potential needed for polymerization of oligofurans (compared to furan) is a key factor in achievement of improved properties of polyfurans reported in this work. DFT calculations and experiments show that polyfurans are much more rigid than polythiophenes, and alkyl substitution does not disturb backbone planarity and conjugation. The obtained properties of polyfuran films are similar or superior to the properties of electrochemically prepared poly(oligothiophene)s under similar conditions.     

New regiosymmetrical dioxopyrrolo- and dihydropyrrolo-functionalized polythiophenes

[structure: see text] We present the synthesis of two N-alkylated poly(dioxopyrrolothiophene)s and two N-alkylated poly(dihydropyrrolothiophene)s with potential application in the field of conducting polymers. The polymers are synthesized from the corresponding 2,5-dibromothiophenes by an Ullmann-type polymerization and a Stille-type polymerization, respectively. The two N-alkylated poly(dihydropyrrolothiophene)s are the first examples of amino-functionalized polythiophenes built from regiosymmetrical thiophene monomers.     

Kumada chain-growth polycondensation as a universal method for synthesis of well-defined conjugated polymers

Kumada chain-growth polycondensation (KCGP) is a novel method for the synthesis of well-defined conjugated polymers. Because the Ni-catalyst can transfer in an intramolecular process to the propagating chain end, the polymerization follows chain-growth mechanism. With this newly developed method, various conjugated polymers, such as polythiophenes, poly(p-phenylene) (PPP), polypyrrole (PPy), and polyfluorene with controlled molecular weights and relatively narrow polydispersities (PDIs), have been prepared. Especially, the polymerizations for poly(3-alkylthiophene)s (P3ATs), PPP, and PPy exhibited quasi-living characteristics, which allows preparing polymer brushes, fully-conjugated block copolymers, and macroinitiators and macro-reactants for the synthesis of rod-coil block copolymers. In the current review, the progress in this new area is summarized.     

Synthesis and nonlinear optical properties of high glass transition poly(maleimide-4-phenylstyrene)s

Nonlinear optical polymers with high T_g were prepared by polymer analogous reaction of maleic anhydride copolymers with aminoalkyl-functionalized azo chromophores. Poled films of the polymers show a good nonlinear optical response that is stable at temperatures up to 125°C.