Solvent effects on low-lying absorptions and vibrational spectra of thieno[3,4-b]pyrazines: the role of unconventional C–H···N bonds

  • Marcos V. A. Damasceno
  • Vinícius Manzoni
  • Lucas Modesto-Costa
  • Geanso M. Moura
  • Jordan Del Nero
  • Alberto Torres
  • Rodrigo GesterEmail author
Original Paper


Difunctionalized thieno[3,4-b]pyrazines are a class of fused-ring systems used as precursors for copolymers and since these molecules were first synthesized, there is a long discussion about their photophysics and vibrational properties. For 2,3-dimethylthieno[3,4-b]pyrazine, different degrees of solvation were combined to determine how the environment tunes these molecular properties, which can allow future applications. The present results indicate that unconventional C–H···N hydrogen bonds have great influence in both UV–Vis and IR spectra. The low-energy region is composed by two close nπ* and ππ* absorptions, with the lowest excitation being associated with an nπ* line. This absorption is covered by an intense ππ* explaining the reason why nπ* absorptions were never observed for these polymeric compounds. Another effect of the weak C–H···N bond is to tune the highest vibrational frequencies corresponding to C–H stretching modes of the solute’s methyl groups providing strong and uncommon blueshifts of ~ 15 cm−1 and better stabilizing the solute in the liquid environment.


UV–Vis spectra Vibrational frequencies Unconventional hydrogen bond Solvent effects 



This work was supported by the following Brazilian financial agencies: CNPq, CAPES, and FAPEAL.


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© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Faculdade de Ciências Biológicas, Agrárias, Engenharia e da SaúdeUniversidade Estadual de Mato GrossoTangará da SerraBrazil
  2. 2.Instituto de FísicaUniversidade Federal de AlagoasMaceióBrazil
  3. 3.Departamento de QuímicaInstituto Militar de EngenhariaRio de JaneiroBrazil
  4. 4.Instituto de Geociências e EngenhariaUniversidade Federal do Sul e Sudeste do ParáMarabáBrazil
  5. 5.Faculdade de FísicaUniversidade Federal do ParáBelémBrazil
  6. 6.Departmento de FísicaUniversidade Federal de Santa CatarinaFlorianópolisBrazil
  7. 7.Faculdade de FísicaUniversidade Federal do Sul e Sudeste do ParáMarabáBrazil

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