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Electronic properties of poly(thiophene-3-methyl acetate)

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Abstract

The electronic structure of poly(thiophene-3-methyl acetate) has been investigated using UV–vis absorption spectroscopy and quantum mechanical calculations. Experimental measures in chloroform solution indicate that the π-conjugation length increases with the polymer concentration, which is reflected by the red shift of the absorbance peak of the π-π* transition. On the other hand, the energy required for the π-π* transition has been found to decrease with the volatility of the solvent for concentrated polymer solutions, even though the influence of the solvent is very small for dilute solutions. Quantum mechanical calculations indicate that the interactions between the π-conjugated backbone and the methyl acetate side groups are very weak. On the other hand, the lowest energy transition predicted for an infinite polymer chain that adopts the anti-gauche and all-anti conformations is 2.8 and 1.9 eV, respectively. Finally, measurements on spin-casted nanofilms reflect that the π-π* transition energy increases with the thickness, which has been attributed to the distortion of the molecular conformation. In spite of this, the energy gap obtained for the thinnest film (1.52 eV) is significantly smaller than that determined for dilute and concentrated chloroform solutions (2.56 and 2.09 eV, respectively).

The π-conjugation length and the energy required for the π-π* transition of poly(thiophene-3-methyl acetate) have been examined in different environments (i.e. gas-phase, dilute and concentrated solutions considering solvents with different polarity and volatility, and spin-casted nanofilms) using a combination of UV-vis spectroscopy and quantum mechanical calculations.

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Acknowledgements

This work has been supported by MICINN and FEDER (Grant MAT2009-09138), by the Generalitat de Catalunya (research group 2009 SGR 925 and XRQTC). Computer resources were generously provided by the “Centre de Supercomputació de Catalunya” (CESCA). A.G. acknowledges financial support from the Euro Brasilian Windows agency (Grant No. 41309-EM-1-2008-PT-ERAMUNDUS-ECW-L16) for his 6-month stay at the UPC. Support for the research of C.A. was received through the prize “ICREA Academia” for excellence in research funded by the Generalitat de Catalunya.

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Authors and Affiliations

  1. Departament d’Enginyeria Química, E.T.S d’Enginyers Industrials de Barcelona, Universitat Politècnica de Catalunya, Diagonal 647, Barcelona, 08028, Spain

    Alex L. Gomes, Elaine Armelin & Carlos Alemán

  2. Departamento de Tecnologia de Polímeros, Faculdade de Engenharia Química, Universidade Estadual de Campinas, Avenida Albert Einstein nº 500, Barão Geraldo, CEP 13083-852, Campinas, SP, Brazil

    Alex L. Gomes & João Sinézio de C. Campos

  3. Departament de Química, Escola Politècnica Superior, Universitat de Lleida, c/Jaume II n°69, Lleida, 25001, Spain

    Jordi Casanovas

  4. Departament de Física Aplicada, E.U.E.T.I.I., Universitat Politècnica de Catalunya, Pça Rei 15, Igualada, 08700, Spain

    Oscar Bertran

  5. Center for Research in Nano-Engineering, Universitat Politècnica de Catalunya, Campus Sud, Edifici C’, C/Pasqual i Vila s/n, Barcelona, 08028, Spain

    Elaine Armelin & Carlos Alemán

Authors
  1. Alex L. Gomes
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  2. Jordi Casanovas
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  3. Oscar Bertran
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  4. João Sinézio de C. Campos
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  5. Elaine Armelin
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  6. Carlos Alemán
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Correspondence to Elaine Armelin or Carlos Alemán.

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Gomes, A.L., Casanovas, J., Bertran, O. et al. Electronic properties of poly(thiophene-3-methyl acetate). J Polym Res 18, 1509–1517 (2011). https://doi.org/10.1007/s10965-010-9556-4

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  • DOI: https://doi.org/10.1007/s10965-010-9556-4

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