Dearomatization Approach Toward a Superbenzoquinone-Based Diradicaloid, Tetraradicaloid, and Hexaradicaloid
Dr. Guangwu Li
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYa Zou
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorJohnathan Joo Cheng Lee
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Yong Ni
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorCorresponding Author
Prof. Jishan Wu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Guangwu Li
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYi Han
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorYa Zou
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorJohnathan Joo Cheng Lee
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorDr. Yong Ni
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorCorresponding Author
Prof. Jishan Wu
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
Search for more papers by this authorAbstract
Reported here is the step-by-step dearomatization of a highly aromatic polycyclic aromatic hydrocarbon (PAH), the hexa-peri-hexabenzocoronene (also called as “superbenzene”), to give a series of superbenzoquinones containing two, four, and six ketone groups. Different from traditional PAH-based quinones, these superbenzoquinones show open-shell multiradical character by rearomatization in the open-shell forms as experimentally validated by X-ray crystallographic analysis, NMR and ESR spectroscopy, and FT-IR measurements, as well as theoretically supported by restricted active space spin-flip calculations. These compounds exhibit structure- and molecular-symmetry-dependent optical, electrochemical, and magnetic properties.
Conflict of interest
The authors declare no conflict of interest.
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References
- 1
- 1aS. P. Roche, J. A. Porco, Jr., Angew. Chem. Int. Ed. 2011, 50, 4068; Angew. Chem. 2011, 123, 4154;
- 1bY. Li, S. Zhu, J. Li, A. Li, J. Am. Chem. Soc. 2016, 138, 3982;
- 1cG. Zhao, G. Xu, C. Qian, W. Tang, J. Am. Chem. Soc. 2017, 139, 3360.
- 2
- 2aC. Song, X. Ma, Appl. Catal. B 2003, 41, 207;
- 2bS. Khan, S. Gupta, N. Gupt, Biotechnol. Lett. 2018, 40, 1329.
- 3
- 3a“Chloranil”: D. R. Buckle in Encyclopedia of Reagents for Organic Synthesis, Wiley, New York, 2001;
- 3bW. Brown, A. B. Turner, J. Chem. Soc. C 1971, 2566.
- 4B. Huskinson, M. P. Marshak, C. Suh, S. Er, M. R. Gerhardt, C. J. Galvin, X. Chen, A. Aspuru-Guzik, R. G. Gordon, M. J. Aziz, Nature 2014, 505, 195.
- 5
- 5aH. Zolllinger, Color Chemistry, 3rd ed., Wiley-VCH, Weinheim, 2001;
- 5bH.-S. Bien, J. Stawitz, K. Wunderlich, Anthraquinone dyes and intermediates, Ulmann's Encyclopedia of Industrial Chemistry, Vol. 3, Wiley-VCH, Weinheim, 2012, p. 513.
- 6
- 6aK. Dimroth, W. Umbach, K. H. Blocher, Angew. Chem. Int. Ed. Engl. 1963, 2, 620;
10.1002/anie.196306203 Google ScholarAngew. Chem. 1963, 75, 861;
- 6bL. A. Wendling, R. West, J. Org. Chem. 1978, 43, 1573;
- 6cE. D. Wellman, K. R. Lassila, R. West, J. Org. Chem. 1984, 49, 965;
- 6dK. Takahashi, T. Suzuki, J. Am. Chem. Soc. 1989, 111, 5485;
- 6eR. West, J. A. Jorgenson, K. L. Stearly, J. C. Calabrese, J. Chem. Soc. Chem. Commun. 1991, 1234;
- 6fP. Boldt, D. Bruhnke, F. Gerson, M. Scholz, P. G. Jones, F. Bar, Helv. Chim. Acta 1993, 76, 1739;
- 6gH. Kuata, T. Tanaka, M. Oda, Chem. Lett. 1999, 28, 749;
- 6hT. Takahashi, K. Matsuoka, K. Takimiya, T. Otsubo, Y. Aso, J. Am. Chem. Soc. 2005, 127, 8928;
- 6iR. Ponce Ortiz, J. Casado, V. Hernández, J. T. L. Navarrete, P. M. Viruela, E. Ortí, K. Takimiya, T. Otsubo, Angew. Chem. Int. Ed. 2007, 46, 9057; Angew. Chem. 2007, 119, 9215;
- 6jK. Zhang, K. Huang, J. Li, J. Luo, C. Chi, J. Wu, Org. Lett. 2009, 11, 4854;
- 6kS. Di Motta, F. Negri, D. Fazzi, C. Castiglioni, E. V. Canesi, J. Phys. Chem. Lett. 2010, 1, 3334;
- 6lA. Ueda, S. Nishida, K. Fukui, T. Ise, D. Shiomi, K. Sato, T. Takui, K. Nakasuji, Y. Morita, Angew. Chem. Int. Ed. 2010, 49, 1678; Angew. Chem. 2010, 122, 1722;
- 6mE. V. Canesi, D. Fazzi, L. Colella, C. Bertarelli, C. Castiglioni, J. Am. Chem. Soc. 2012, 134, 19070;
- 6nD. Schmidt, M. Son, M. J. Lim, M.-J. Lin, I. Krummenacher, H. Braunschweig, D. Kim, F. Wurthner, Angew. Chem. Int. Ed. 2015, 54, 13980; Angew. Chem. 2015, 127, 14186;
- 6oH. Wei, L. Zhang, H. Phan, X. Huang, T. S. Herng, J. Zhou, W. Zeng, J. Ding, S. Luo, J. Wu, Z. Zeng, Chem. Eur. J. 2017, 23, 9419;
- 6pK. Naoda, D. Shimizu, O. J. Kim, K. Furukawa, D. Kim, A. Osuka, Chem. Eur. J. 2017, 23, 8969;
- 6qS. Lee, F. Miao, H. Phan, T. S. Herng, J. Ding, J. Wu, D. Kim, ChemPhysChem 2017, 18, 591;
- 6rR. Rausch, D. Schmidt, D. Bialas, I. Krummenacher, H. Braunschweig, F. Würthner, Chem. Eur. J. 2018, 24, 3420–3424;
- 6sF. Miao, H. Phan, J. Wu, Molecules 2019, 24, 1446.
- 7
- 7aT. M. Pappenfus, R. J. Chesterfield, C. D. Frisbie, K. R. Mann, J. Casado, J. D. Raff, L. L. Miller, J. Am. Chem. Soc. 2002, 124, 4184;
- 7bR. J. Chesterfield, C. R. Newman, T. M. Pappenfus, P. C. Ewbank, M. H. Haukaas, K. R. Mann, L. L. Miller, C. D. Frisbie, Adv. Mater. 2003, 15, 1278;
- 7cS. Handa, E. Miyazaki, K. Takimiya, Y. Kunugi, J. Am. Chem. Soc. 2007, 129, 11684;
- 7dD. E. Janzen, M. W. Burand, P. C. Ewbank, T. M. Pappenfus, H. Higuchi, D. A. da Silva Filho, V. G. Young, J. L. Brédas, K. R. Mann, J. Am. Chem. Soc. 2004, 126, 15295;
- 7eJ. C. Ribierre, T. Fujihara, S. Watanabe, M. Matsumoto, T. Muto, A. Nakao, T. Aoyama, Adv. Mater. 2010, 22, 1722;
- 7fC. Zhang, X. Zhu, Acc. Chem. Res. 2017, 50, 1342;
- 7gD. Yuan, D. Huang, S. M. Rivero, A. Carreras, C. Zhang, Y. Zou, X. Jiao, C. R. McNeill, X. Zhu, C.-A. Di, D. Zhu, D. Casanova, J. Casado, Chem 2019, 5, 864;
- 7hD. Yuan, Y. Guo, Y. Zeng, Q. Fan, J. Wang, Y. Yi, X. Zhu, Angew. Chem. Int. Ed. 2019, 58, 4958; Angew. Chem. 2019, 131, 5012.
- 8
- 8aS. Patai, The Chemistry of Quinonoid Compound, Wiley, London, 1974;
- 8bS. M. Arabei, T. A. Pavich, J. Appl. Spectrosc. 2000, 67, 236;
- 8cJ. Zhang, D. Zhu, M. Matsuo, Polymer 2008, 49, 5424;
- 8dM. Desroches, J.-F. Morin, Chem. Eur. J. 2018, 24, 2858.
- 9
- 9aE. Clar, The Aromatic Sextet, Wiley, London, 1972;
- 9bA. Konishi, Y. Hirao, M. Nakano, A. Shimizu, E. Botek, B. Champagne, D. Shiomi, K. Sato, T. Takui, K. Matsumoto, H. Kurata, T. Kubo, J. Am. Chem. Soc. 2010, 132, 11021;
- 9cZ. Sun, S. Lee, K. Park, X. Zhu, W. Zhang, B. Zheng, P. Hu, Z. Zeng, S. Das, Y. Li, C. Chi, R. Li, K. Huang, J. Ding, D. Kim, J. Wu, J. Am. Chem. Soc. 2013, 135, 18229.
- 10
- 10aJ. Wu, W. Pisula, K. Müllen, Chem. Rev. 2007, 107, 718;
- 10bB. A. G. Hammer, K. Müllen, Chem. Rev. 2016, 116, 2103;
- 10cM. Stępień, E. Gońka, M. Żyła, N. Sprutta, Chem. Rev. 2017, 117, 3479.
- 11G. Li, H. Phan, T. S. Herng, T. Y. Gopalakrishna, C. Liu, W. Zeng, J. Ding, J. Wu, Angew. Chem. Int. Ed. 2017, 56, 5012; Angew. Chem. 2017, 129, 5094.
- 12R. Yamaguchi, S. Hiroto, H. Shinokubo, Org. Lett. 2012, 14, 2472.
- 13X. Li, F. Yang, Y. Wu, RSC Adv. 2014, 4, 13738.
- 14D. Lungerich, J. F. Hitzenberger, M. Marcia, F. Hampel, T. Drewello, N. Jux, Angew. Chem. Int. Ed. 2014, 53, 12231; Angew. Chem. 2014, 126, 12427.
- 15CCDC 1920677, 1920743, 1920744, and 1920745 (5, 15, 19 and SBQ-6O) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
- 16J. Kruszewski, T. M. Krygowski, Tetrahedron Lett. 1972, 13, 3839.
- 17D. Geuenich, K. Hess, F. Kohler, R. Herges, Chem. Rev. 2005, 105, 3758.
- 18P. v. R. Schleyer, C. Maerker, A. Dransfeld, H. J. Jiao, N. J. R. van Eikema Hommes, J. Am. Chem. Soc. 1996, 118, 6317.
- 19
- 19aM. Abe, Chem. Rev. 2013, 113, 7011;
- 19bZ. Sun, Z. Zeng, J. Wu, Acc. Chem. Res. 2014, 47, 2582;
- 19cZ. Zeng, X. Shi, C. Chi, J. T. L. Navarrete, J. Casado, J. Wu, Chem. Soc. Rev. 2015, 44, 6578;
- 19dT. Kubo, Chem. Lett. 2015, 44, 111;
- 19eT. Y. Gopalakrishna, W. Zeng, X. Lu, J. Wu, Chem. Commun. 2018, 54, 2186.
- 20B. Bleaney, K. D. Bowers, Proc. R. Soc. London Ser. A 1952, 214, 451.
- 21
- 21aD. Casanova, M. Head-Gordon, Phys. Chem. Chem. Phys. 2009, 11, 9779;
- 21bS. Das, T. S. Herng, J. L. Zafra, P. M. Burrezo, M. Kitano, M. Ishida, T. Y. Gopalakrishna, P. Hu, A. Osuka, J. Casado, J. Ding, D. Casanova, J. Wu, J. Am. Chem. Soc. 2016, 138, 7782;
- 21cX. Lu, S. Lee, J. O. Kim, T. Y. Gopalakrishna, H. Phan, T. S. Herng, Z. L. Lim, Z. Zeng, J. Ding, D. Kim, J. Wu, J. Am. Chem. Soc. 2016, 138, 13048;
- 21dX. Lu, S. Lee, Y. Hong, H. Phan, T. Y. Gopalakrishna, T. S. Herng, T. Tanaka, M. E. Sandoval-Salinas, W. Zeng, J. Ding, D. Casanova, A. Osuka, D. Kim, J. Wu, J. Am. Chem. Soc. 2017, 139, 13173.
- 22
- 22aK. Yamaguchi, T. Fueno, H. Fukutome, Chem. Phys. Lett. 1973, 22, 461;
- 22bK. Yamaguchi in Self-Consistent Field: Theory and Applications (Eds.: ), Elsevier, Amsterdam, 1990, p. 727;
- 22cM. Head-Gordon, Chem. Phys. Lett. 2003, 372, 508;
- 22dT. Minami, M. Nakano, J. Phys. Chem. Lett. 2012, 3, 145.
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