Skip to main content
Log in

Modeling p-type charge transport in thienoacene analogs of pentacene

Theoretical Chemistry Accounts Aims and scope Submit manuscript


The charge transport properties of two fused-ring thienoacenes, (a) the syn-isomer of dibenzo-thieno-dithiophene (DBTDT), packing in the solid state with a π–π stacking arrangement and also known as bis-benzo-thieno-thiophene (BBTT) and (b) C6-DBTDT, an alkylated derivative, packing in the more conventional herring-bone arrangement, are investigated computationally in the framework of the non-adiabatic hopping mechanism. Charge transfer rate constants are computed within the Marcus–Levich–Jortner formalism including a single effective mode treated quantum mechanically and are injected in a kinetic Monte Carlo scheme to propagate the charge carrier in the crystal. Charge mobilities are computed at room temperature with and without the influence of an electric field and are shown to compare very well with the measured mobilities in single-crystal devices. Both systems show an almost 1D charge transport with C6-DBTDT displaying about a ten times larger mobility value, in agreement with experiment. It is shown that the role of the HOMO-1 orbital is not relevant for BBTT, while it might contribute to a more marked 2D charge transport character for C6-DBTDT.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5


  1. Jiang W, Li Y, Wang Z (2013) Heteroarenes as high performance organic semiconductors. Chem Soc Rev 42:6113–6127

    Article  CAS  Google Scholar 

  2. Li R, Hu W, Liu Y, Zhu D (2010) Micro-and nanocrystals of organic semiconductors. Acc Chem Res 43:529–540

    Article  CAS  Google Scholar 

  3. Takimiya K, Shinamura S, Osaka I, Miyazaki E (2011) Thienoacene-based organic semiconductors. Adv Mater 23:347–4370

    Article  CAS  Google Scholar 

  4. Takimiya K, Osaka I, Mori T, Nakano M (2014) Organic semiconductors based on [1]benzothieno[3,2-b][1]benzothiophene substructure. Acc Chem Res 47:1493–1502

    Article  CAS  Google Scholar 

  5. Barbarella G, Zambianchi M, Bongini A, Antolini L (1993) The deformability of the thiophene ring—a key to the understanding of the conformational properties oligophenes and polythiophenes. Adv Mater 5:834–838

    Article  CAS  Google Scholar 

  6. Li R, Dong H, Zhan X, He Y, Li H, Hu W (2010) Single crystal ribbons and transistors of a solution processed sickle-like fused-ring thienoacene. J Mater Chem 20:6014–6018

    Article  CAS  Google Scholar 

  7. Li R, Jiang L, Meng Q, Gao J, Li H, Tang Q, He M, Hu W, Liu Y, Zhu D (2009) Micrometer-sized organic single crystals, anisotropic transport, and field-effect transistors of a fused-ring thienoacene. Adv Mater 21:4492–4495

    Article  CAS  Google Scholar 

  8. Li R, Dong H, Zhan X, Li H, Wen SH, Deng WQ, Han KL, Hu W (2011) Physicochemical, self-assembly and field-effect transistor properties of anti- and syn-thienoacene isomers. J Mater Chem 21:11335

    Article  CAS  Google Scholar 

  9. Miyata Y, Yoshikawa E, Minari T, Tsukagoshi K, Yamaguchi S (2012) High-performance organic field-effect transistors based on dihexyl-substituted dibenzo[d, d’]thieno[3,2-b;4,5-b’]dithiophene. J Mater Chem 22:7715–7717

    Article  CAS  Google Scholar 

  10. He P, Tu Z, Zhao G, Zhen Y, Geng H, Yi Y, Wang Z, Zhang H, Xu C, Liu J, Lu X, Fu X, Zhao Q, Zhang X, Ji D, Jiang L, Dong H, Hu W (2015) Tuning the crystal polymorphs of alkyl thienoacene via solution self-assembly toward air-stable and high-performance organic field-effect transistor. Adv Mater 27:825–830

    Article  CAS  Google Scholar 

  11. Di Donato E, Fornari RP, Di Motta S, Li Y, Wang ZH, Negri F (2010) n-Type charge transport and mobility of fluorinated perylene bisimide semiconductors. J Phys Chem B 114:5327–5334

    Article  CAS  Google Scholar 

  12. Di Motta S, Siracusa M, Negri F (2011) Structural and thermal effects on the charge transport of core-twisted chlorinated perylene bisimide semiconductors. J Phys Chem C 115:20754–20764

    Article  CAS  Google Scholar 

  13. Canola S, Negri F (2014) Anisotropy of the n-type charge transport and thermal effects in crystals of a fluoro-alkylated naphthalene diimide: a computational investigation. Phys Chem Chem Phys 16:21550–21558

    Article  CAS  Google Scholar 

  14. Canola S, Negri F (2015) Role of the HOMO-1 orbital on the p-type charge transport of the fused ring thienoacene DBTDT. J PhysChem C 119:11499–11505

    CAS  Google Scholar 

  15. Bredas JL, Beljonne D, Coropceanu V, Cornil J (2004) Charge transfer and energy transfer in pi conjugated oligomers and polymers: a molecular picture. Chem Rev 104:4971–5003

    Article  CAS  Google Scholar 

  16. Coropceanu V, Cornil J, da Silva Filho DA, Olivier Y, Silbey R, Bredas JL (2007) Charge transport in organic semiconductors. Chem Rev 107:926–952

    Article  CAS  Google Scholar 

  17. Frisch M J, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowsk J, Fox DJ Gaussian09, Revision D01 (Gaussian Inc, 2009)

  18. Troisi A (2011) Charge transport in high mobility molecular semiconductors: classical models and new theories. Chem Soc Rev 40:2347–2358

    Article  CAS  Google Scholar 

  19. Troisi A, Cheung DL (2008) Modelling charge transport in organic semiconductors: from quantum dynamics to soft matter. Phys Chem Chem Phys 10:5941–5952

    Article  CAS  Google Scholar 

  20. Jortner J (1976) Temperature dependent activation energy for electron transfer between biological molecules. J Chem Phys 64:4860–4867

    Article  CAS  Google Scholar 

  21. Barbara PF, Meyer TJ, Ratner MA (1996) Contemporary issues in electron transfer research. J Phys Chem 100:13148–13168

    Article  CAS  Google Scholar 

  22. Troisi A, Orlandi G (2001) The hole transfer in DNA: calculation of electron coupling between close bases. Chem Phys Lett 344:509–518

    Article  CAS  Google Scholar 

  23. Valeev EF, Coropceanu V, da Silva Filho DA, Salman S, Bredas JL (2006) Effect of electronic polarization on charge transport parameters in molecular organic semiconductors. J Am Chem Soc 128:9882–9886

    Article  CAS  Google Scholar 

  24. Löwdin PO (1950) On the non-orthogonality problem connected with the use of atomic wave functions in the theory of molecules and crystals. J Chem Phys 18:365–375

    Article  Google Scholar 

  25. Baumeier B, Kirkpatrick J, Andrienko D (2010) Density functional determination of intermolecular charge transfer properties for large scale morphologies. Phys Chem Chem Phys 12:11103–11113

    Article  CAS  Google Scholar 

  26. McMahon DP, Troisi A (2010) Evaluation of the external reorganization energy of polyacenes. J Phys Chem Lett 1:941–946

    Article  CAS  Google Scholar 

  27. Fichthorn KA, Weinberg WH (1991) Theoretical foundations of dynamical Monte Carlo simulations. J Chem Phys 95:1090–1096

    Article  CAS  Google Scholar 

  28. Di Motta S, Di Donato E, Negri F, Orlandi G, Fazzi D, Castiglioni C (2009) Resistive molecular memories: influence of molecular parameters on the electrical bistability. J Am Chem Soc 131:6591–6598

    Article  CAS  Google Scholar 

  29. Stehr V, Pfister J, Fink RF, Engels B, Deibel C (2011) First-principles calculations of anisotropic charge-carrier mobilities in organic semiconductor crystals. Phys Rev B 83:155208

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations


Corresponding author

Correspondence to Fabrizia Negri.

Additional information

Published as part of the special collection of articles “CHITEL 2015 - Torino - Italy”.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 1416 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Canola, S., Pecoraro, C. & Negri, F. Modeling p-type charge transport in thienoacene analogs of pentacene. Theor Chem Acc 135, 33 (2016).

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: