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 POLYMERIZATION OF 5-CYANOINDOLE IN MIXED ELECTROLYTES OF BORON TRIFLUORIDE DIETHYL ETHERATE AND DIETHYL ETHER

High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） and diethyl ether （EE） （by volume 1：1） ＋ 0,05 mol L^-1 Bu4NBF4. The film formed can be peeled off the electrode into freestanding films, The addition of EE into BFEE can improve the solubility of monomer. P5CI films obtained from this medium showed excellent electrochemical behavior with conductivity of 10^-2 S cm^-1, Structural studies showed that the polymerization of 5-cyanoindole occurred at the 2,3 position. As-formed P5CI films were thoroughly soluble in strong polar organic solvent dimethyl sulfoxide （DMSO） while partly soluble in tetrahydrofuran （THF） or acetone. Fluorescence spectral studies indicated that P5CI was a good blue-ight emitter.

Capacitive properties of low potential electro-polymerized polyfluorene and activated carbon composite electrode

Polyfluorene (PF) film has been successfully electropolymerized at lower potential (0.91 V vs.Ag/AgCl) in the mixed electrolyte of boron trifluoride diethyl etherate and trifluoroacetic acid.The PF film is characterized to have about 10 repeat units and no presence of ketonic defect site.UV-vis and photoluminescent spectral studies indicate that the PF film is blue light emitting.From cyclic voltammetry and galvanostatic charge-discharge tests in 1 M lithium perchlorate/acetonitrile electrolyte,the polyfluorene/activated carbon electrode shows a specific capacitance of 227.1 F g-1 (per active layer mass) and reversible redox reaction at the potential of 1.4 V in a three electrode configuration.An asymmetric electrochemical capacitor based on this composite electrode and activated carbon electrode exhibits a specific energy of 14.7 Wh kg-1 (per active layer mass).These results indicate that electrochemically prepared polyfluorene could be used as energy storage component for electrochemical application.

LOW-POTENTIAL ELECTROSYNTHESIS OF CONDUCTING AND ELECTROACTIVE OLIGOCATECHOLBORANE WITH BLUE LIGHT-EMITTING PROPERTIES

Novel conducting oligocatecholborane （OCOB） with electrical conductivity of 3.73 × 10^-2 S cm-1 was successfully synthesized by low-potential electropolymerization of catecholborane （COB） in boron trifluoride diethyl etherate at 0.70 V versus Ag/AgC1. FT-IR and ^1H-NMR spectra, together with the computational results, proved that COB was polymerized through the coupling at C（4） and C（5} positions and the reactive B- H bond was stable during the electrochemical polymerization. The resulting product was mainly composed of oligomers with short chain lengths by GPC and mass spectral results. The as-formed OCOB film showed good electrochemistry in monomer-free electrolytes with the electrochromic property from opaque blue to sap green. Fluorescence studies indicated that soluble OCOB can emit bright blue light under excitation of 365 nm UV light with the maximum emission at 396 nm and a fluorescence quantum yield of 0.21. The deposited OCOB also exhibited favorable thermal stability and smooth and compact morphology even at high magnifications.

AN ELECTROCHEMICALLY PREPARED SKY-BLUE LIGHT EMITTING ETHER FUNCTIONALIZED POLYFLUORENE AS CHEMOSENSOR FOR METAL IONS

Synthesis and electrochemical polymerization of 9,9-bis（2-（2-（2-methoxy ethoxy）ethoxy）ethyl）-fluorene （EO-F） into poly[9,9-bis（2-（2-（2-methoxy ethoxy）ethoxy）ethyl）-fluorene] （EO-PF） films are reported. The boron trifluoride diethyl etherate electrolyte enables facile preparation of EO-PF films at lower potential compared to LiCIOa/MeCN and the electrochemical polymerizations are discussed. The EO-PF shows good electrochemical behavior and can be dissolved in solvents such as DMSO and THF. The solubility of EO-PF in THF is 2 mg.mL-1 and the number average molecular weight is 35300 with a polydispersity index of 1.65. The side chains on C9 position of the monomer maintain unchanged aRer electrooxidation into corresponding polymer. The EO-PF dissolved in THF under 365 nm ultraviolet light is sky blue light emitting with the Commission Internationale de L＇Eclairage-CIE coordinates of （0.19, 0.15）. The electropolymerized EO-PF is used for the first time in chemosensing metal ions, demonstrating fluorescence quenching for Mn2＋ and Fe3＋ while fluorescence enhancement for Cr6＋ ions.