Vibrational properties of poly(arylene vinylene)s

Buisson, Jean‐Pierre; Lefrant, S.; Louarn, G.; Mevellec, Jean‐Yves; Orion, I.; Eckhardt, H.

doi:10.1016/0379-6779(92)90103-p

Cited by 10 publications

(6 citation statements)

References 9 publications

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“…35,36 In Raman, the pristine polymer spectrum as shown in Figure 3 is dominated by multiple modes around 1600 cm -1 . 37,38 There are at least four distinct modes in this feature, with the dominant one centered at 1592 cm -1 . These have been assigned to stretches within the phenyl ring.…”

Section: Resultsmentioning

confidence: 97%

“…This broadness has been attributed to the presence of metallic tubes 27 as well as the large diameter range of the sample as seen earlier in Figure in the UV/vis/NIR spectrum. The vibrational spectroscopy of PmPV has been well explored. , In Raman, the pristine polymer spectrum as shown in Figure is dominated by multiple modes around 1600 cm -1 . , There are at least four distinct modes in this feature, with the dominant one centered at 1592 cm -1 . These have been assigned to stretches within the phenyl ring .…”

Section: Resultsmentioning

confidence: 99%

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Spectroscopic Analysis of Single-Walled Carbon Nanotubes and Semiconjugated Polymer Composites

Sm¹,

Tg²,

Gregan³

et al. 2004

J. Phys. Chem. B

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Interactions between arc discharge single-walled carbon nanotubes within polymer composites have been well documented. Here hybrid systems of the conjugated organic polymer poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene) (PmPV) and HiPco SWNTs are explored using UV/vis/NIR and Raman spectroscopy at 514.5 and 632.8 nm to determine specific interactions. An examination of the radial breathing modes at 514.5 nm shows similar tube diameters of 1.28 and 1.35 nm selected for both the arc discharge and HiPco composites. The corresponding G lines of both composites show no specific type of tubes being selected. At 514.5 nm, the G line of the HiPco composite (1% mass fraction) shows contributions from semiconducing and metallic tubes, and the arc discharge composite (1% mass fraction) is dominated by semiconducting nanotubes. At 632.8 nm, the G line of the HiPco composite (1% mass fraction) is dominated by semiconducting tubes, and the arc discharge composite (1% mass fraction) shows strong contributions from metallic tubes. This finding is a strong indication that the selection process is dependent on tube diameter rather than backbone structure. The solubility limits of both composites are determined by investigating the G lines of both composites and have been found to be greater than 1% mass fraction by weight for the arc discharge composite and greater than 0.1% mass fraction by weight for the HiPco composite.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Spectroscopic Analysis of Single-Walled Carbon Nanotubes and Semiconjugated Polymer Composites

Sm¹,

Tg²,

Gregan³

et al. 2004

J. Phys. Chem. B

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“…These temperature values were chosen in order to spectroscopically capture the transition in the region of 50 °C in the DSC of the raw polymer. At both temperatures, the PmPV spectrum is dominated by multiple modes around 1600 cm -1 , which have been assigned to stretches within the phenyl ring. − The mode at 1630 cm -1 has been assigned to the trans -vinylene stretch on the backbone and is common to most PPV-based polymers, , while the feature at 1577 cm -1 is attributed to cis contributions in this polymer .…”

Section: Resultsmentioning

confidence: 99%

“…At both temperatures, the PmPV spectrum is dominated by multiple modes around 1600 cm -1 , which have been assigned to stretches within the phenyl ring. [27][28][29] The mode at 1630 cm -1 has been assigned to the trans-vinylene stretch on the backbone and is common to most PPV-based polymers, 27,30 while the feature at 1577 cm -1 is attributed to cis contributions in this polymer. 30 In cycle 1, upon increase in temperature the modes of the PmPV spectrum decrease in intensity due to the inherent temperature dependence of the Stokes spectrum in Raman, although the trans-vinylene mode at 1630 cm -1 increases in relative intensity, whereas the cis-vinylene mode at 1577 cm -1 decreases in relative intensity, as shown in Figure 3.…”

Section: Resultsmentioning

confidence: 99%

Temperature-Induced Nucleation of Poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene) Crystallization by HiPco Single-Walled Carbon Nanotubes

et al. 2005

J. Phys. Chem. B

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Hybrid systems of the conjugated organic polymer poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene)(PmPV) and HiPco single-walled carbon nanotubes (SWNTs) are explored using spectroscopic and thermal techniques to determine specific interactions. Vibrational spectroscopy indicates a weak interaction, and this is further elucidated using differential scanning calorimetry (DSC), confocal laser scanning microscopy, temperature-dependent Raman spectroscopy, and temperature-dependent infrared spectroscopy of the raw materials and the composite. An endothermic transition is observed in the DSC of both the polymer and the 0.1% HiPco composite in the region of 50 degrees C. Also observed in the DSC of the composite is a double-peaked endotherm at -39 and -49 degrees C, which does not appear in the polymer. The Raman spectroscopy of the polymer upon increasing the temperature to 60 degrees C shows a diminished cis-vinylene mode at 1575 cm(-1), with an increase in relative intensity of the trans-vinylene mode at 1630 cm(-1). Partially irreversible change in isomerization suggests increased order in the polymer. This change in the polymer is also manifest in the Raman composite spectrum upon increase of the temperature to 60 degrees C, where the spectrum becomes abruptly dominated by nanotubes. Raman spectroscopy of the composite shows no change at -35 degrees C; however, infrared absorption measurements suggest that the transition at -35 degrees C derives from the polymer side chains. Here the composite at -35 degrees C shows a change in the absorbance of the polymer side chain aryl-oxide linkage at 1250 cm(-1) and alkyl-oxide stretch at 1050 cm(-1). Infrared spectra thus suggest that the transitions in the lower temperature region around -35 degrees C are side chain-induced, while Raman spectra suggest that the transition at 60 degrees C is backbone-induced. Furthermore, temperature cycling induces an irreversible decrease in the mean fluorescence intensity of the polymer, coupled with a further reduction in the mean fluorescence intensity of the composite. This suggests that an increase in crystallization of the composite is supported and enhanced by an increase in ordering of the polymer. Implications are discussed.

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“…This shoulder corresponds to the CC stretching of vinylene in doped MEH-PPV, and it is notable that the band at 1621 cm –1 , associated with the CC stretching of vinylene in neutral MEH-PPV, diminishes as a result. , Vibrational modes that are coupled to the π-electron system exhibit remarkable sensitivity to these modifications, which can indicate a partial (incomplete) conversion of undoped MEH-PPV from a benzoid structure to a quinoid structure during the p-doping process (see Figure S6). The bands at 1307 and 1283 cm –1 , which correspond to phenyl CC interring stretch and CC–H bending in neutral MEH-PPV, exhibit downshifts to 1288 and 1258 cm –1 , respectively, upon doping. ,, The peak assignments for both the neutral and doped active materials are summarized in Table . Electrochemical doping results in significant differences between the ordered and disordered domains within conducting polymer films, as reported in previous studies .…”

Section: Results and Discussionmentioning

confidence: 99%

In Situ Surface-Enhanced Raman Spectroscopy on Organic Mixed Ionic-Electronic Conductors: Tracking Dynamic Doping in Light-Emitting Electrochemical Cells

Jafari,

Pedersen,

Barhemat

et al. 2024

ACS Appl. Mater. Interfaces

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In the domain of organic mixed ionic−electronic conductors (OMIECs), simultaneous transport and coupling of ionic and electronic charges are crucial for the function of electrochemical devices in organic electronics. Understanding conduction mechanisms and chemical reactions in operational devices is pivotal for performance enhancement and is necessary for the informed and systematic development of more promising materials. Surface-enhanced Raman spectroscopy (SERS) is a potent tool for monitoring electrochemical evolution and dynamic doping in operational devices, offering enhanced sensitivity to subtle spectral changes. We demonstrate the utility of SERS for in situ tracking of doping in OMIECs in an organic light-emitting electrochemical cell (LEC) containing a conjugated polymer (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]; MEH-PPV), a molecular anion (lithium triflate), and an electrolyte network (poly(ethylene oxide); PEO). SERS enhancement is achieved via an interleaved layer of gold particles formed by spontaneous breakup of a deposited thin gold film. The results successfully highlight the ability of SERS to unveil time-resolved MEH-PPV doping and polaron formation, elucidating the effects of triflate ion transfer in the operating device and validating the electrochemical doping model in LECs.

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Vibrational properties of poly(arylene vinylene)s

Cited by 10 publications

References 9 publications

Spectroscopic Analysis of Single-Walled Carbon Nanotubes and Semiconjugated Polymer Composites

Spectroscopic Analysis of Single-Walled Carbon Nanotubes and Semiconjugated Polymer Composites

Temperature-Induced Nucleation of Poly(p-phenylene vinylene-co-2,5-dioctyloxy-m-phenylene vinylene) Crystallization by HiPco Single-Walled Carbon Nanotubes

In Situ Surface-Enhanced Raman Spectroscopy on Organic Mixed Ionic-Electronic Conductors: Tracking Dynamic Doping in Light-Emitting Electrochemical Cells

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