Article

Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals

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Abstract

The consequence of unpaired electrons in organic molecules has fascinated and confounded chemists for over a century. The study of open-shell molecules has been rekindled in recent years as new synthetic methods, improved spectroscopic techniques and powerful computational tools have been brought to bear on this field. Nonetheless, it is the intrinsic instability of the biradical species that limits the practicality of this research. Here we report the synthesis and characterization of a molecule based on the diindeno[b,i]anthracene framework that exhibits pronounced open-shell character yet possesses remarkable stability. The synthetic route is rapid, efficient and possible on the gram scale. The molecular structure was confirmed through single-crystal X-ray diffraction. From variable-temperature Raman spectroscopy and magnetic susceptibility measurements a thermally accessible triplet excited state was found. Organic field-effect transistor device data show an ambipolar performance with balanced electron and hole mobilities. Our results demonstrate the rational design and synthesis of an air- and temperature-stable biradical compound.

  • Compound

    9,10-Bis((triisopropylsilyl)ethynyl)-2,7-dibromoanthracene

  • Compound

    9,10-Bis((triisopropylsilyl)ethynyl)-2,7-bis(2'-formylphenyl)anthracene

  • Compound

    Dihydro-DIAn

  • Compound

    ((8,16-Dimesityldiindeno[1,2-b:1',2'-i]anthracene-6,14-diyl)bis(ethyne-2,1-diyl))bis(triisopropylsilane)

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Acknowledgements

This work was supported by the US National Science Foundation (CHE-1301485), by the Spanish Government, MINECO (CTQ2012-33733 and CTQ2011-26507), by Junta de Andalucía (P09-FQM-4708) and Generalitat Valenciana (PrometeoII/2014/076), by a Japan Society for the Promotion of Science (JSPS) Research Fellowship for Young Scientists (No. 15J04949), Grant-in-Aid for Scientific Research (A) (No. 25248007) from the JSPS, a Grant-in-Aid for Scientific Research on Innovative Areas ‘Stimuli-Responsive Chemical Species’ (No. A24109002a), ‘π-System Figuration’ (15H00999), ‘Photosynergetics’ (A26107004a), the Strategic Programs for Innovative Research, Ministry of Education, Culture, Sports, Science & Technology, Japan, the Computational Materials Science Initiative, Japan, the Swedish Research Council (project grant 621-2011-4177) and the Swedish National Infrastructure for Computation (NSC, Linköping). K.J. and H.O. thank R. Herges for providing the AICD 2.0.0 program. The authors acknowledge the Biomolecular Mass Spectrometry Core of the Environmental Health Sciences Core Center at Oregon State University (NIH P30ES000210). We thank T. Kubo (Osaka) for insightful discussions.

Author information

Affiliations

  1. Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA

    • Gabriel E. Rudebusch
    • , Jonathan L. Marshall
    •  & Michael M. Haley
  2. Department of Physical Chemistry, University of Malaga, Campus de Teatinos s/n, 229071 Malaga, Spain

    • José L. Zafra
    • , Iratxe Arrechea-Marcos
    • , Guzmán L. Espejo
    • , Rocío Ponce Ortiz
    •  & Juan Casado
  3. Department of Chemistry – BMC, Uppsala University, Box 576, Uppsala 751 23, Sweden

    • Kjell Jorner
    •  & Henrik Ottosson
  4. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan

    • Kotaro Fukuda
    •  & Masayoshi Nakano
  5. Instituto de Ciencia Molecular, Universidad de Valencia, 46980 Paterna, Valencia, Spain

    • Carlos J. Gómez-García
  6. CAMCOR, University of Oregon, Eugene, Oregon 97403-1433, USA

    • Lev N. Zakharov

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Contributions

G.E.R. conceived the project, and designed and carried out the experiments, analysed the data and wrote the manuscript. M.M.H. played a critical role in the discussion of the experimental design, project direction, experiments and results, and in the preparation of the manuscript. J.L.M. acquired and analysed the CV data. I.A.M., G.L.E. and R.P.O. obtained the OFET data. L.N.Z. acquired and analysed the X-ray crystallographic data. J.L.Z. performed the Raman spectroscopic measurements. C.G.G. performed the SQUID experiments. J.C. interpreted the magnetic and spectroscopic data and co-wrote the paper. K.F. and M.N. performed the calculation and discussed the geometry optimization, the open-shell character and the S–T gaps. K.J. performed the ACID and NICS-XY density functional theory calculations, and, together with H.O., analysed the data from these computations. All the authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Masayoshi Nakano or Henrik Ottosson or Juan Casado or Michael M. Haley.

Supplementary information

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Crystallographic information files

  1. 1.

    Supplementary information

    Crystallographic data for compound DIAn.