Journal of Polymer Research

, 19:9972 | Cite as

Theoretical studies on the electronic structures and optical properties of the thiophene oligomer containing 2-(trifluoromethyl) thieno [3, 4-b] thiophene moiety and the CF3 end-caps

Original Paper


Structural, electronic, and optical properties of a series of π-conjugated thiophene oligomers P1-P3 and CF 3 P1-CF 3 P3 have been theoretically investigated. P1-P3 contain the 2- (trifluoromethyl) thieno [3, 4-b] thiophene moiety as the centre and 1–3 repeating thiophene units adjacent to its two sides respectively, while their corresponding derivatives CF 3 P1-CF 3 P3 with the CF3 as end-caps. The geometric structures of the oligomers in the ground and excited state were optimized by PBE1PBE and CIS methods with 6–31G (d) basis sets, respectively. All the oligomers exhibit zigzag arrangements. The absorptions and emissions were calculated by the time-dependent density functional theory method (TD-PBE1PBE). The lowest-lying absorptions of all the oligomers can be characterized as π-π* electron transition. For each series of oligomers, there is a progressive lowering in HOMO-LUMO gap with the increase of the repeating unit, being consistent with the red-shifted trend in the lowest-lying absorption and fluorescence from P1 to P3 and CF 3 P1 to CF 3 P3. To compare the P- and corresponding CF 3 P-oligomers, the end-cap CF3 group causes the slight blue shifts in absorption and emission spectra. The ionization potentials (IPS), electron affinities (EAs), and reorganization energies (λ) as well as the hole/electron extraction energies (HEP/EEP) of the oligomers were explored and those of the corresponding polymer were obtained by extrapolation method. The IP and HEP of P-polymer are lower than those of CF 3 P-polymer, indicating that the P-polymer is more suitable for hole transport than CF 3 P-polymer, while the higher EA and EEP for CF 3 P-polymer suggest the better electron transfer property. For CF3 end-caps, the CF 3 P-polymer exhibits the equal reorganization energy between electron and hole, which is a precondition for the charge transfer balance.


Conjugated polymer Absorption Fluorescence Electronic structure 



This work was supported by the Natural Science Foundation of China (Grant No. 20973076, 21003057 and 21173096) and Specialized Research Fund for the Doctoral Program of Higher Education (20110061110018).

Supplementary material

10965_2012_9972_MOESM1_ESM.docx (28 kb)
ESM 1 (DOCX 27 kb)


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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  1. 1.State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical ChemistryJilin UniversityChangchunPeople’s Republic of China
  2. 2.College of ChemistryJilin UniversityChangchunPeople’s Republic of China

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