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Title: Infrared and multi-wavelength Raman spectroscopy of regio-regular P3HT and its deutero derivatives

Abstract

The recently synthesized regio–regular poly(3–hexylthiophene–2,5–diyl) selectively deuterated on the main chain backbone and/or on the hexyl side chain have given the opportunity to record their infrared (IR) and Raman spectra, and to carry out a spectroscopic study supported by density functional theory calculations. The Effective Conjugation Coordinate associated with the collective C=C stretching mode, with Raman scattering and IR absorption near 1,450 cm–1, is used as a probe of the electronic structure and the molecular conformation of the chain backbone. With the help of the data collected from the deuterated species, the vibrational assignment for the structurally relevant 1,600–1,300 cm–1 region has been clarified. The excitation–dependent wavenumbers and intensities of the C=C stretching Raman modes are discussed. Raman spectra excited in–resonance or off–resonance show the existence of a multimodal distribution of effective conjugation lengths that are ascribed to a phase hairy–A with a practically flat backbone chain, a phase hairy–B where the conformation of the backbone is slightly distorted, and an amorphous phase. As a result, IR spectra provide additional information on the Effective Conjugation Coordinate.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2];  [1]
+ Show Author Affiliations
  1. Politecnico di Milano, Milan (Italy)
  2. Univ. de Málaga, Málaga (Spain)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1523765
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Raman Spectroscopy
Additional Journal Information:
Journal Volume: 49; Journal Issue: 3; Journal ID: ISSN 0377-0486
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; deutero derivatives; DFT; effective conjugation coordinate; P3HT; poly(3‐hexylthiophene‐2,5‐diyl)

Citation Formats

Brambilla, Luigi, Capel Ferrón, C., Tommasini, M., Hong, Kunlun, López Navarrete, J. T., Hernández, V., and Zerbi, G. Infrared and multi-wavelength Raman spectroscopy of regio-regular P3HT and its deutero derivatives. United States: N. p., 2017. Web. doi:10.1002/jrs.5301.
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Brambilla, Luigi, Capel Ferrón, C., Tommasini, M., Hong, Kunlun, López Navarrete, J. T., Hernández, V., & Zerbi, G. Infrared and multi-wavelength Raman spectroscopy of regio-regular P3HT and its deutero derivatives. United States. https://doi.org/10.1002/jrs.5301
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Brambilla, Luigi, Capel Ferrón, C., Tommasini, M., Hong, Kunlun, López Navarrete, J. T., Hernández, V., and Zerbi, G. Fri . "Infrared and multi-wavelength Raman spectroscopy of regio-regular P3HT and its deutero derivatives". United States. https://doi.org/10.1002/jrs.5301. https://www.osti.gov/servlets/purl/1523765.
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@article{osti_1523765,
title = {Infrared and multi-wavelength Raman spectroscopy of regio-regular P3HT and its deutero derivatives},
author = {Brambilla, Luigi and Capel Ferrón, C. and Tommasini, M. and Hong, Kunlun and López Navarrete, J. T. and Hernández, V. and Zerbi, G.},
abstractNote = {The recently synthesized regio–regular poly(3–hexylthiophene–2,5–diyl) selectively deuterated on the main chain backbone and/or on the hexyl side chain have given the opportunity to record their infrared (IR) and Raman spectra, and to carry out a spectroscopic study supported by density functional theory calculations. The Effective Conjugation Coordinate associated with the collective C=C stretching mode, with Raman scattering and IR absorption near 1,450 cm–1, is used as a probe of the electronic structure and the molecular conformation of the chain backbone. With the help of the data collected from the deuterated species, the vibrational assignment for the structurally relevant 1,600–1,300 cm–1 region has been clarified. The excitation–dependent wavenumbers and intensities of the C=C stretching Raman modes are discussed. Raman spectra excited in–resonance or off–resonance show the existence of a multimodal distribution of effective conjugation lengths that are ascribed to a phase hairy–A with a practically flat backbone chain, a phase hairy–B where the conformation of the backbone is slightly distorted, and an amorphous phase. As a result, IR spectra provide additional information on the Effective Conjugation Coordinate.},
doi = {10.1002/jrs.5301},
journal = {Journal of Raman Spectroscopy},
number = 3,
volume = 49,
place = {United States},
year = {2017},
month = {12}
}
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Journal Article:
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https://doi.org/10.1002/jrs.5301
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Figures / Tables:

Figure 1 Figure 1: On the left chemical structure of the translational repeating unit for rr-P3HT; on the right indication of the deuterated derivatives.
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