Organic Letters
Letter
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as well as solvent molecules. However, this crystal structure has
an R factor as large as 21% due to the disordered orientation of
C60 molecules. Such a large R factor does not allow us to analyze
molecular packing in the cocrystal with high accuracy. Further
studies on characterization and application of the cocrystals of 1
and C60 are in progress in our laboratory.
In summary, we developed a convenient synthesis of
tetrabenzo[7]circulene (1) which, upon minor modification,
was also useful for synthesis of thiophene-annulated [7]-
circulenes. DFT calculation indicates that the most stable
conformers of 1 are two enantiomers of the C2 symmetry, which
interconvert fast at room temperature. In agreement with the
calculation, 1 exists in the crystal as two enantiomers having a
twisted-saddle shape close to the C2 symmetry. X-ray
crystallography also reveals that the [7]circulene moiety in 1 is
more curved than [7]circulene itself. It is found that 1 functions
as a p-type semiconductor in thin-film transistors and is able to
cocrystallize with C60, an n-type semiconductor.
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ASSOCIATED CONTENT
* Supporting Information
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̈
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(17) Xiao, S.; Myers, M.; Miao, Q.; Sanaur, S.; Pang, K.; Steigerwald,
M.; Nuckolls, C. Angew. Chem., Int. Ed. 2005, 44, 7390.
(18) Sakamoto, Y.; Suzuki, T. J. Am. Chem. Soc. 2013, 135, 14074.
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Whalley, A. C. Chem. - Eur. J. 2014, 20, 3705. (b) Miller, R. W.; Averill, S.
E.; Van Wyck, S. J.; Whalley, A. C. J. Org. Chem. 2016, 81, 12001.
(20) Our recent attempts to synthesize hepta-peri-heptabenzo-[7]
ciruculene were not successful. See: Yang, X.; Miao, Q. Synlett 2016, 27,
2091.
S
The Supporting Information is available free of charge on the
Details of synthesis and characterization; crystallographic
data for 1 and 4; fabrication and characterization of
organic thin film transistors; NMR spectra (PDF)
X-ray data for compound 1 (CIF)
X-ray data for compound 4 (CIF)
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AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
(27) Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic
Chemistry; University Science Books: Sausalito, CA, 2004; Chapter 7.
(28) Feng, C.-N.; Hsu, W.-C.; Li, J.-Y.; Kuo, M.-Y.; Wu, Y.-T. Chem. -
Eur. J. 2016, 22, 9198.
ACKNOWLEDGMENTS
■
We thank Ms. Hoi Shan Chan (The Chinese University of Hong
Kong) for the single-crystal crystallography. This work was
supported by the Research Grants Council of Hong Kong (CRF
C4030-14G) and The Chinese University of Hong Kong
(Faculty of Science Strategic Development Scheme and the
One-Off Funding for Research from Research Committee).
(29) Laudise, R. A.; Kloc, C.; Simpkins, P. G.; Siegrist, T. J. Cryst.
Growth 1998, 187, 449.
(30) HOMO = −5.10 eV − Eox (versus Fc+/Fc). See: Cardona, C. M.;
Li, W.; Kaifer, A. E.; Stockdale, D.; Bazan, G. C. Adv. Mater. 2011, 23,
2367.
(31) Xu, X.; Yao, Y.; Shan, B.; Gu, X.; Liu, D.; Liu, J.; Xu, J.; Zhao, N.;
Hu, W.; Miao, Q. Adv. Mater. 2016, 28, 5276.
(32) Liu, D.; He, Z.; Su, Y.; Diao, Y.; Mannsfeld, S. C. B.; Bao, Z.; Xu, J.;
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