STRUCTURAL ANALYSIS AND ENVIRONMENTAL STABILITY OF POLYFLUORINATED GROUP SUBSTITUTED POLYTHIOPHENES

Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes gives polymers with relatively high molecular weights and good processibility. Investigation of these polymers by means of GPC indicates that an increase in the number of fluorine atoms in the fluorinated group results in a decrease in degree of polymerization of the polymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluorinated 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 polymers do. Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric, electrochemical and thermal stability.

Synthesis and Characterization of Polythiophenes Bearing Diphenyl Groups in the Conjugated Chain

4,4＇-dibromo-2-nitro-biphenyl and 4,4＇-dibromo-2,3＇-dinitro-biphenyl have been synthesized via nitration reaction with 4,4＇-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4＇-di（4-hexyl-thiophen-2-yl）biphenyl, 4,4＇-di（4-hexyl-thiophen-2-yl）-2- nitro-biphenyl and 4,4＇-di（4- hexyl-thiophen-2-yl）-2,3＇-dinitrobiphenyl were synthesized through Stille coupling reaction, followed by polymerization in the presence of FeC13, respectively. UV-vis absorption spectra, fluorescence spectra, photoluminescence spectra and electrochemical properties of the polymers were investigated. And the band-gap （Eg）, HOMO orbital energy （EHCMO）, and LUMO orbital energy （EUJMO） of the polymers were calculated. Among the polymers, polymer PBTN and PBTD show lower band-gap （2.67 and 2.63 eV）, lower HOMO energy level （-5.38 and -5.4 eV） and broader wavelength （432 and 438 nm） than that of polymer PBTB （2.69 eV, -5.36 eV and 424 nm） with incorporation of one nitro group or two nitro groups in the main chain, respectively.

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

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the electrochemical polymerization of thiophene monomers and properties of the obtained polymers were analyzed. The introduction of a fluoroether functional group at the 3-position of the thiophene ring leads to an increase of the oxidation potential of the monomer and to a decrease of the conductivity of the resulting polymers, even with the use of a CH2 group as spacer. Conversely, the presence of an oxygen atom directly at the 3-position of the thiophene ring, which offsets the negative withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conducting polythiophenes.

A comparative study on p-doping behavior of polythiophenes with CH_3SO_3H

Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.

A minimized fluorescent chemosensor array utilizing carboxylate-attached polythiophenes on a chip for metal ions detection

Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.

New conducting polythiophenes containing substituted polyfluorinated alkoxy chain

A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.

Low-temperature NO_2 sensors based on polythiophene/WO_3 organic-inorganic hybrids

Polythiophene （PTP） was prepared by a chemical oxidative polymerization and nanosized WO3 was prepared by a colloidal chemical method. The organic-inorganic PTP/WO3 hybrids with different mass fractions of PTP were obtained by a simple mechanically mixing the prepared PTP and WO3. The as-prepared PTP/WO3 hybrids have a higher thermal stability than the pure PTP. The gas sensing measurements demonstrate that the PTP/WO3 hybrid sensors exhibit higher response for detecting NO2 at low temperature than the pure PTP and WO3 sensor. The sensing mechanism is suggested to be related to the existence of p-n heterojunctions in the PTP/WO3 hybrids. The response of the PTP/WO3 hybrids is markedly influenced by the PTP mass fraction. The 20% PTP/WO3 hybrid shows high response and good selectivity to NO2 at low temperature （〈90℃）. Therefore, the PTP/WO3 hybrids can be expected to be potentially used as gas sensor material for detecting NO2 at low temperature.

ELECTROCHEMICAL COPOLYMERIZATION OF 3-(4-FLUOROPHENYL)THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.

ELECTROCHEMICAL COPOLYMERIZATION OF DIBENZOFURAN AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...

Electrochemical Synthesis of Polythiophene in an Ionic Liquid

Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.

DEFORMATION MEASUREMENT OF CON-DUCTING POLYTHIOPHENE THIN FILMS BY AN ELECTRONIC SPECKLE PATTERN INTERFEROMETRIC METHOD

The deformation measurement of electrosynthesized polythiophene(Pth) thin films is difficult because of the small thickness and highflexibility of the specimen. An electronic speckle patterninterferom- etry (ESPI) method is used to measure the deformation ofPth films of thicknesses in the range of 4-65 μm . Theirstress-strain curves are obtained. It is found that the mechanicalproperties of Pth films are sensitive to the specimen thickness. Thetensile strength increases with decreasing thickness of thin filmfrom 10 μm. The influence of the electrochemical synthesisconditions on the mechanical properties of Pth films is also dis-Cussed.

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.

LOW POTENTIAL ELECTROPOLYMERIZATION OF ANISOTROPIC CONDUCTIVE POLYTHIOPHENE FILMS AND FABRICATION OF ELECTRICAL DEVICES

The Complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF3-ethyl ether (BFEE) remarkedly lowered the electrochemical polymerization potential. The positively charged metal surface of electrode in the process of electrochemical deposition enhanced the coordination interaction between pi-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surface of electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transfer integrals, the transport of charge is believed to be principally along the conjugated chains, which is much greater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thickness is more than 10(4) times than that along the surface plane of the film. In this paper we review the recent development of polymerization technique by low potential electrochemical method performed in our lab and several electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, and laminate film junction of undoped polythiophene derivatives were used.

Synthesis and Characterization of Poly(N-Hexyl-2, 7-di(2-(4-hexylthiophene)carbazole)

One conjugated polymer consisting of carbazole and 3-hexylthiophene moiety, poly(N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole)(PNDC), has been synthesized by ferric chloride oxidative polymerization. The monomer N-Hexyl-2,7-di(2-(4-hexylthiophene)carbazole was synthesized and characterized by IR, 1H-NMR, 13C-NMR and MS. UV-vis absorption spectrum, fluorescence spectrum, photoluminescence spectrum and electrochemical properties of the polymer were investigated. Polymer PNDC shows maximum peak appearing at 394 nm in UV-vis absorption spectrum, strongest fluorescence-emission at 482 nm in fluorescence spectrum and maximum emission peak at 492 nm in photoluminescence spectrum. The band-gap(Eg), HOMO energy(EHOMO), and LUMO energy(ELUMO) of the polymer were obtained as 2.58,-5.32, and-2.74 e V, respectively.

Charge and spin-dependent thermal efficiency of polythiophene molecular junction in presence of dephasing

The charge and spin-dependent thermoelectric properties of different lengths of polythiophene in a molecular junction are investigated using the B ¨uttiker probe method within Green function formalism in linear response regime. The coupling of the molecular chain to three-dimensional ferromagnetic electrodes is described by a tight-binding model for both parallel and antiparallel spin configurations. The decrease of height of transmission probability peaks and thermoelectric coefficients are observed in the presence of the B ¨uttiker probes. The reduction is more intensive in the strong dephased chains.Results show that the spin magnetothermopower is bigger than the charge magnetothermopower due to the larger difference between the spin thermopowers with respect to the charge ones. In addition, we observed that the kind of carriers participating in the thermoelectric transport depends on the number of the thiophene rings.

INFRARED EMISSIVITY OF CONDUCTING POLYMERS

The infrared emissivity of conducting polymers in 8—20μm and at 50—150℃ in the direction of normal line has been measured as a function of wavelength, conductivity at room temperature, counterion, doping levels, measuring temperature and thickness of sample.

In-situ Microscopic FT-IR Spectroelectrochemical Investigation of Polythiophene Film Modified Electrode

A polythiophene film was electrochemically deposited on a Pt micro plate electrode and investigated by cyclic voltammetry and in situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electropolymerization of thiophene on the Pt surface was affected by the surface adsorption processes of thiophene molecules. Two adsorption modes were identified. Two structure models of the polythiophene chain were observed simultaneously. It was proposed that the good conductibility of the polythiophene film was originated from a co vibratory equilibrium of the link part of model Ⅰ and model Ⅱ.

Polythiophene encapsulated inside(13, 0) CNT: A nano-hybrid system

We present a first-principles calculation on the electronic and optical properties of a hybrid nanotube system consisting of a （13, 0） single-walled carbon nanotube encapsulated by polythiophene. This hybrid-system represents a complete new type of matter and is known as the peapod system. We analyze bow the polythiophene changes the electronic and optical properties of the nanotube. In particular, we examine new features in the dielectric function due to the transitions between the states of the polymer and the nanotube. The electronic structure of the combined system appears to be a simple superposition of the individual constituents. The density functional theory calculations demonstrate van der Waals interaction as the bonding mechanism between the tube and the encapsulated molecule.

Analysis of Eigenvalues for Molecular Structures

In this article,we study different molecular structures such as Polythiophene network,PLY(n)for n=1,2,and 3,Orthosilicate(Nesosilicate)SiO4,Pyrosilicates(Sorosilicates)Si2O7,Chain silicates(Pyroxenes)(SiO3)n,and Cyclic silicates(Ring Silicates)Si3O9 for their cardinalities,chromatic numbers,graph variations,eigenvalues obtained from the adjacency matrices which are square matrices in order and their corresponding characteristics polynomials.We convert the general structures of these chemical networks in to mathematical graphical structures.We transform the molecular structures of these chemical networks which are mentioned above,into a simple and undirected planar graph and sketch them with various techniques of mathematics.The matrices obtained from these simple undirected graphs are symmetric.We also label the molecular structures by assigning different colors.Their graphs have also been studied for analysis.For a connected graph,the eigenvalue that shows its peak point(largest value)obtained from the adjacency matrix has multiplicity 1.Therefore,the gap between the largest and its smallest eigenvalues is interlinked with some form of“connectivity measurement of the structural graph”.We also note that the chemical structures,Orthosilicate(Nesosilicate)SiO4,Pyrosilicates(Sorosilicates)Si2O7,Chain silicates(Pyroxenes)(SiO3)n,and Cyclic silicates(Ring Silicates)Si3O9 generally have two same eigenvalues.Adjacency matrices have great importance in the field of computer science.

Development of Conducting Polythiophene

Polythiophene and its derivatives are getting more andmore attention as a new kind of conducting polymers.Their conductivity,application,possible processingmethods and development are discussed in this article.