A solid-state NMR investigation of the dopability of poly(p-phenylene vinylene) model compounds and corresponding polymers with iodine

Nouwen, J; Adriaensens, Peter; Franco, Dirk; Vanderzande, Dirk; Martens, H.; Gelan, Jan; Yang, Z.; Geise, H.J.

doi:10.1016/0379-6779(92)90057-p

Cited by 9 publications

(3 citation statements)

References 25 publications

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“…However, these blends are characteristically inhomogeneous. 13 To improve the homogeneity of such blends, we initiated a study of novel multiblock copolymers that consist of substituted PV blocks and conventional polymer blocks. The PV blocks can be doped and produce electrically conducting species14 and can be used as light-emitting chromophores.…”

Section: Introductionmentioning

confidence: 99%

Intrinsically soluble copolymers with well-defined alternating substituted p-phenylenevinylene and ethylene oxide blocks

Yang¹,

Karasz²,

Geise³

1993

Macromolecules

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Three new copolymers with well-defined alternating substituted p-phenylenevinylene (PV) and ethylene oxide (EO) blocks were studied. The multiblock copolymers were synthesized using the Wittig reaction and characterized with GPC, IR, elemental analysis, and 13C and NMR. Thermal properties were studied with DSC and the results compared with those of blends of a model compound and polyethylene oxide). The copolymers are intrinsically soluble and fusible, and free-standing films can be cast from chloroform solutions. Iodine doping of the films from vapor or in solution yields materials with electrical conductivities in the range of 10-3 S cm-1.

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Section: Introductionmentioning

confidence: 99%

Intrinsically soluble copolymers with well-defined alternating substituted p-phenylenevinylene and ethylene oxide blocks

Yang¹,

Karasz²,

Geise³

1993

Macromolecules

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“…5 Poly͑p-phenylene vinylene͒ ͑PPV, see Diagram 1͒ has attracted a considerable amount of interest in recent years because of its excellent processibility, 6 mechanical properties, 7 good electrical conductivity, 8 and its ability to exhibit electroluminescence 9 and photoluminescence. 10 Although a variety of chemical [11][12][13][14][15][16][17] and electrochemical [18][19][20][21][22][23][24][25] doping studies have been performed on this polymer, an in situ study of mass uptake during vapor-phase doping and the simultaneous resistance change ͑conductivity change͒ has not been reported. Most significantly, the dopant level at maximum conductivity can only be determined from an in situ study such as this.…”

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confidence: 99%

Vapor-Phase Fuming Sulfuric Acid-Doped Poly(p-phenylene vinylene) as a Potential Humidity Sensor

Shah

Hanson

Arbuckle-Keil

2001

J. Electrochem. Soc.

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Vapor-phase doping of poly͑p-phenylene vinylene͒ ͑PPV͒ with fuming sulfuric acid has been investigated using the quartz crystal microbalance. Thin films of PPV were obtained on quartz crystal substrates by spin casting a precursor polymer, which is thermally converted to give the PPV product. Dopant mass uptake and the resistance of the film were recorded in situ during doping. A decrease in the resistance and therefore an increase in the conductivity of the film from the insulating to the metallic regime was observed. Mass uptake information was used to determine the dopant concentration at the maximum conductivity, the doping rate, and the diffusion coefficient of the polymer. The dopant concentration results were verified by Rutherford backscattering spectrometry and elemental analysis. The observation that the doped material tends to lose its metallic properties upon exposure to moisture in the atmospheric air has been used to investigate its potential as a humidity-sensing device. The golden metallic appearance of the film changes as well. The conductivity can be returned by application of a dynamic vacuum. Fuming sulfuric acid-doped films were exposed to a range of relative humidities, from 4 to 75%. A rapid and significant linear response ͑over four orders of magnitude͒ to all percent humidities was observed. Fuming sulfuric acid-doped PPV may have the potential for applications as a humidity sensor or as a disposable shut-off switch in moisture-sensitive devices.

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“…Under these conditions, the oligo(p-phenylenevinylene) model compound MPV is obtained as a mixture of the cis,cis-isomer (34%), the &,trans-isomer (46%) and the trans,trans-isomer (20%). Because of its high solubility (16,4 g/100 mL CHC1,) the mixture is used as such and referred to hereafter simply as MPV.…”

Section: Experimental Partmentioning

confidence: 99%

Miscibility of an oligo(p‐phenylenevinylene) with polystyrene studied by solid‐state nuclear magnetic resonance

Nouwen¹,

Adriaensens²,

Gelan³

et al. 1994

Macro Chemistry & Physics

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Molecular proximity of cidtrans mixtures of 2,5-dimethoxy-l,4-bis[2-(3,4,5-trimethoxyphenyl)vinyl]benzene (MPV, 1) and polystyrene (PS) in mixtures of different MPV/PS weight ratios up to 60/40 is shown by 'H combined rotation and multiple pulse spectroscopy (CRAMPS) using 2D exchange experiments. The MPV/PS mixtures up to a weight ratio 60140 are homogeneous, whereas the mixture with a weight ratio MPV/PS = 80/20 is heterogeneous. The comparison of the cross polarization/magic angle spinning (CP/MAS) 13C NMR spectra of pure MPV and of MPV mixed with PS shows significant linebroadening in case of intimate mixing, while the heterogeneous mixture shows some extra finestructure. The miscibility results were confirmed by proton spin-locking relaxation time measurements (T,,H) on the mixtures. On intimate mixing, T,,H is averaged out and varies linearly as a function of the composition of the mixture. CRAMPS-spectra and T,,H measurements show that iodine-doped MPV/PS mixtures (weight ratios 40/60 and 60/40) are heterogeneous. Furthermore, doping causes a slight proton chemical shift change and reduces the Tl ,H-values of those oligomer-polymer systems.

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A solid-state NMR investigation of the dopability of poly(p-phenylene vinylene) model compounds and corresponding polymers with iodine

Cited by 9 publications

References 25 publications

Intrinsically soluble copolymers with well-defined alternating substituted p-phenylenevinylene and ethylene oxide blocks

Intrinsically soluble copolymers with well-defined alternating substituted p-phenylenevinylene and ethylene oxide blocks

Vapor-Phase Fuming Sulfuric Acid-Doped Poly(p-phenylene vinylene) as a Potential Humidity Sensor

Miscibility of an oligo(p‐phenylenevinylene) with polystyrene studied by solid‐state nuclear magnetic resonance

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