Abstract
Herein we present novel Raman spectroscopic studies carried out for polyselenophene (PSe), poly(3,4-ethylenedioxyselenophene) (PEDOS), and alkyl-substituted poly(alkyl-3,4-ethylenedioxyselenophene) (PEDOS-Cn: n=2, 8, and 12) homologues. These spectroscopic data are combined with morphological and structural analysis techniques, such as AFM, and DFT simulations. An investigation into the extent of π-conjugation in PSe is presented by comparing its spectral signatures with those of a homologous series of oligoselenophenes. Our experimental data suggest that π-conjugation in the PSe backbone extends to more than six selenophene units. The incorporation of ethylenedioxy (EDO) groups in PEDOS results in a more complex spectrum and a downshift of the C-C/C-C stretching vibration (or effective conjugation coordinate (ECC) mode); this provides evidence for an improvement in the π-conjugational properties along the PSe backbone upon EDO substitution. The dispersity of π-conjugation lengths in different PEDOS samples obtained through different synthetic routes is evaluated as a function of different structural factors. Finally, we present experimental evidence that the insertion of alkyl chains into the EDO units slightly impacts on the π-conjugational properties of the PEDOS backbone in the non-annealed samples (with an improved π-electron delocalization found in PEDOS-C8), but moderately affects the degree of molecular order of polymer films upon thermal annealing.
| Original language | English |
|---|---|
| Pages (from-to) | 759-766 |
| Number of pages | 8 |
| Journal | Israel Journal of Chemistry |
| Volume | 54 |
| Issue number | 5-6 |
| DOIs | |
| Publication status | Published - 2014 |
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Keywords
- conjugation
- heterocycles
- polymers
- Raman spectroscopy
- thermochemistry
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Raman spectroscopic characterization of polyselenophenes and poly(3,4-ethylenenedioxyselenophene)s. / Ferrõn, Cristina Capel; Sheynin, Yana; Li, Mao; Patra, Asit; Bendikov, Michael; Lõpez Navarrete, Juan T.; Hernández, Victor; Ruiz Delgado, M. Carmen.
In: Israel Journal of Chemistry, Vol. 54, No. 5-6, 2014, p. 759-766.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Raman spectroscopic characterization of polyselenophenes and poly(3,4-ethylenenedioxyselenophene)s
AU - Ferrõn, Cristina Capel
AU - Sheynin, Yana
AU - Li, Mao
AU - Patra, Asit
AU - Bendikov, Michael
AU - Lõpez Navarrete, Juan T.
AU - Hernández, Victor
AU - Ruiz Delgado, M. Carmen
PY - 2014
Y1 - 2014
N2 - Herein we present novel Raman spectroscopic studies carried out for polyselenophene (PSe), poly(3,4-ethylenedioxyselenophene) (PEDOS), and alkyl-substituted poly(alkyl-3,4-ethylenedioxyselenophene) (PEDOS-Cn: n=2, 8, and 12) homologues. These spectroscopic data are combined with morphological and structural analysis techniques, such as AFM, and DFT simulations. An investigation into the extent of π-conjugation in PSe is presented by comparing its spectral signatures with those of a homologous series of oligoselenophenes. Our experimental data suggest that π-conjugation in the PSe backbone extends to more than six selenophene units. The incorporation of ethylenedioxy (EDO) groups in PEDOS results in a more complex spectrum and a downshift of the C-C/C-C stretching vibration (or effective conjugation coordinate (ECC) mode); this provides evidence for an improvement in the π-conjugational properties along the PSe backbone upon EDO substitution. The dispersity of π-conjugation lengths in different PEDOS samples obtained through different synthetic routes is evaluated as a function of different structural factors. Finally, we present experimental evidence that the insertion of alkyl chains into the EDO units slightly impacts on the π-conjugational properties of the PEDOS backbone in the non-annealed samples (with an improved π-electron delocalization found in PEDOS-C8), but moderately affects the degree of molecular order of polymer films upon thermal annealing.
AB - Herein we present novel Raman spectroscopic studies carried out for polyselenophene (PSe), poly(3,4-ethylenedioxyselenophene) (PEDOS), and alkyl-substituted poly(alkyl-3,4-ethylenedioxyselenophene) (PEDOS-Cn: n=2, 8, and 12) homologues. These spectroscopic data are combined with morphological and structural analysis techniques, such as AFM, and DFT simulations. An investigation into the extent of π-conjugation in PSe is presented by comparing its spectral signatures with those of a homologous series of oligoselenophenes. Our experimental data suggest that π-conjugation in the PSe backbone extends to more than six selenophene units. The incorporation of ethylenedioxy (EDO) groups in PEDOS results in a more complex spectrum and a downshift of the C-C/C-C stretching vibration (or effective conjugation coordinate (ECC) mode); this provides evidence for an improvement in the π-conjugational properties along the PSe backbone upon EDO substitution. The dispersity of π-conjugation lengths in different PEDOS samples obtained through different synthetic routes is evaluated as a function of different structural factors. Finally, we present experimental evidence that the insertion of alkyl chains into the EDO units slightly impacts on the π-conjugational properties of the PEDOS backbone in the non-annealed samples (with an improved π-electron delocalization found in PEDOS-C8), but moderately affects the degree of molecular order of polymer films upon thermal annealing.
KW - conjugation
KW - heterocycles
KW - polymers
KW - Raman spectroscopy
KW - thermochemistry
UR - http://www.scopus.com/inward/record.url?scp=84903317633&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84903317633&partnerID=8YFLogxK
U2 - 10.1002/ijch.201400024
DO - 10.1002/ijch.201400024
M3 - Article
AN - SCOPUS:84903317633
VL - 54
SP - 759
EP - 766
JO - Israel Journal of Chemistry
JF - Israel Journal of Chemistry
SN - 0021-2148
IS - 5-6
ER -