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Spectroscopic and electrical characterization of α,γ-bisdiphenylene-β-phenylallyl radical as an organic semiconductor

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Abstract

The semiconductor properties of the earliest known stable radical, α,γ-bisdiphenylene-β-phenylallyl radical (Koelsch radical, 1•) were assessed using spectroscopic and electrical techniques. This radical undergoes reversible redox processes, and it has low redox potentials. In addition, 1• possesses long wavelength absorption bands, owing to the existence of a singly-occupied molecular orbital whose energy level lies between those of the HOMO and LUMO. A spin-coated thin-film of 1• displays photocurrent and an electron mobility of 6.3 × 10−7 cm2 V−1 s−1 on a trially-fabricated organic field effect transistor.

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Notes

  1. For the details, see the Supplementary Material.

  2. As an example of a DFT study of Radicals, see Ref. [22].

  3. The BDPA radical has been commercially available from Aldrich since February 2015. See: www.sigmaaldrich.com/catalog/product/aldrich/152560.

References

  1. J. Fossey, D. Lefort, J. Sorba, Free Radicals in Organic Chemistry (Wiley, New York, 1995)

    Google Scholar 

  2. B. Halliwell, J.M.C. Gutteridge, Free Radicals in Biology and Medicine (Oxford Univ. Press, Oxford, 2015)

    Book  Google Scholar 

  3. G. Moad, D.H. Solomon, The Chemistry of Radical Polymerization, 2nd edn. (Elsevier, Amsterdam, 2006)

    Google Scholar 

  4. R.G. Hicks (ed.), Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds (Wiley, Weinhelm, 2010)

    Google Scholar 

  5. A. Rajca, Chem. Rev. 94, 871 (1994)

    Article  CAS  Google Scholar 

  6. M. Abe, Chem. Rev. 113, 7011 (2013)

    Article  CAS  PubMed  Google Scholar 

  7. C.F. Koelsch, J. Am. Chem. Soc. 54, 3384 (1932)

    Article  CAS  Google Scholar 

  8. C.F. Koelsch, J. Am. Chem. Soc. 54, 4744 (1932)

    Article  CAS  Google Scholar 

  9. C.F. Koelsch, J. Am. Chem. Soc. 79, 4439 (1957)

    Article  CAS  Google Scholar 

  10. Y. Hattori, T. Kusamoto, H. Nishihara, Angew. Chem. Int. Ed. 53, 11845 (2014)

    Article  CAS  Google Scholar 

  11. H. Namai, H. Ikeda, Y. Hoshi, N. Kato, Y. Morishita, K. Mizuno, J. Am. Chem. Soc. 129, 9032 (2007)

    Article  CAS  PubMed  Google Scholar 

  12. H. Ikeda, J. Photopolym. Sci. Technol. 21, 327 (2008)

    Article  CAS  Google Scholar 

  13. H. Namai, H. Ikeda, Y. Hoshi, K. Mizuno, Angew. Chem. Int. Ed. 46, 7396 (2007)

    Article  CAS  Google Scholar 

  14. T. Suga, H. Ohshiro, S. Sugita, K. Oyaizu, H. Nishide, Adv. Mater. 21, 1627 (2009)

    Article  CAS  Google Scholar 

  15. Y. Morita, S. Nishida, T. Murata, M. Moriguchi, A. Ueda, M. Satoh, K. Arifuku, K. Sato, T. Takui, Nat. Mater. 10, 947 (2011)

    Article  CAS  PubMed  Google Scholar 

  16. H. Maruyama, H. Nakano, M. Nakamoto, A. Sekiguchi, Angew. Chem. Int. Ed. 53, 1324 (2014)

    Article  CAS  Google Scholar 

  17. K. Uchida, Z. Mou, M. Kertesz, T. Kubo, J. Am. Chem. Soc. 138, 4665 (2016)

    Article  CAS  PubMed  Google Scholar 

  18. S. Müllegger, M. Rashidi, M. Fattinger, R. Koch, J. Phys. Chem. C 116, 22587 (2012)

    Article  CAS  Google Scholar 

  19. D.D. Eley, K.W. Jones, J.G.F. Littler, M.R. Willis, Trans. Faraday Soc. 63, 902 (1967)

    Article  CAS  Google Scholar 

  20. S.L. Solar, J. Org. Chem. 28, 2911 (1963)

    Article  CAS  Google Scholar 

  21. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, G.A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. Marenich, J. Bloino, B.G. Janesko, R. Gomperts, B. Mennucci, H.P. Hratchian, J.V. Ortiz, A.F. Izmaylov, J.L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V.G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, J.M. Millam, M. Klene, C. Adamo, R. Cammi, J.W. Ochterski, R.L. Martin, K. Morokuma, O. Farkas, J.B. Foresman, and D.J. Fox, Gaussian 09, Revision A.02 (Gaussian, Inc., Wallingford CT) (2016)

  22. Y. Matsui, K. Usui, H. Ikeda, S. Irle, RSC Adv. 8, 83668 (2016)

    Article  CAS  Google Scholar 

  23. D.T. Breslin, M.A. Fox, J. Phys. Chem. 97, 13341 (1993)

    Article  CAS  Google Scholar 

  24. M.M. Matsushita, H. Kawakami, E. Okabe, H. Kouka, Y. Kawada, T. Sugawara, Polyhedron 24, 2870 (2005)

    Article  CAS  Google Scholar 

  25. Y. Wang, H. Wang, Y. Liu, C. Di, Y. Sun, W. Wu, G. Yu, D. Zhang, D. Zhu, J. Am. Chem. Soc. 128, 13058 (2006)

    Article  CAS  PubMed  Google Scholar 

  26. M. Chikamatsu, T. Mikami, J. Chisaka, Y. Yoshida, R. Azumi, K. Yase, A. Shimizu, T. Kubo, Y. Morita, K. Nakasuji, Appl. Phys. Lett. 91, 043506 (2007)

    Article  CAS  Google Scholar 

  27. K. Aoki, H. Akutsu, J. Yamada, S. Nakatsuji, T. Kojima, Y. Yamashita, Chem. Lett. 38, 112 (2009)

    Article  CAS  Google Scholar 

  28. H. Zhang, H. Dong, Y. Li, W. Jiang, Y. Zhen, L. Jiang, Z. Wang, W. Chen, A. Wittmann, W. Hu, Adv. Mater. 28, 7466 (2016)

    Article  CAS  PubMed  Google Scholar 

  29. K. Takagi, T. Nagase, T. Kobayashi, H. Naito, Org. Electron. 15, 372 (2014)

    Article  CAS  Google Scholar 

  30. T. Endo, T. Nagase, T. Kobayashi, K. Takimiya, M. Ikeda, H. Naito, Appl. Phys. Express 3, 121601 (2010)

    Article  CAS  Google Scholar 

  31. T. Nagase, T. Hamada, K. Tomatsu, S. Yamazaki, T. Kobayashi, S. Murakami, K. Matsukawa, H. Naito, Adv. Mater. 22, 4706 (2010)

    Article  CAS  PubMed  Google Scholar 

  32. T. Kushida, T. Nagase, H. Naito, Org. Electron. 12, 2140 (2011)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge valuable discussions with Mr. Yu Suenaga at OPU. This study was partially supported by JSPS KAKENHI grant numbers JP24109009 (Innovative Area Stimuli-responsive Chemical Species), JP17H01265, JP23350023, JP23108718 (pi-Space), JP21108520, JP21655016, and JP19350025. YM also acknowledges the Program to Disseminate Tenure Tracking System, MEXT, Japan.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan

    Yasunori Matsui, Minoru Shigemori, Takuya Ogaki, Eisuke Ohta, Kazuhiko Mizuno & Hiroshi Ikeda

  2. The Research Institute for Molecular Electronic Devices (RIMED), Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan

    Yasunori Matsui, Takuya Ogaki, Eisuke Ohta, Hiroyoshi Naito & Hiroshi Ikeda

  3. Department of Physics and Electronics, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan

    Toshiyuki Endo & Hiroyoshi Naito

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  1. Yasunori Matsui
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Correspondence to Hiroshi Ikeda.

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Matsui, Y., Shigemori, M., Endo, T. et al. Spectroscopic and electrical characterization of α,γ-bisdiphenylene-β-phenylallyl radical as an organic semiconductor. Res Chem Intermed 44, 4765–4774 (2018). https://doi.org/10.1007/s11164-018-3282-7

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