Conformational Planarization versus Singlet Fission: Distinct Excited-State Dynamics of Cyclooctatetraene-Fused Acene Dimers
Takuya Yamakado
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
These authors contributed equally to this work.
Search for more papers by this authorShota Takahashi
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Dr. Kazuya Watanabe
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorProf. Dr. Yoshiyasu Matsumoto
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorProf. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Shohei Saito
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
JST-PRESTO, FRONTIER, Japan
Search for more papers by this authorTakuya Yamakado
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
These authors contributed equally to this work.
Search for more papers by this authorShota Takahashi
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
These authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Dr. Kazuya Watanabe
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorProf. Dr. Yoshiyasu Matsumoto
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorProf. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Shohei Saito
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
JST-PRESTO, FRONTIER, Japan
Search for more papers by this authorAbstract
A set of flapping acene dimers fused with an 8π cyclooctatetraene (COT) ring showed distinct excited-state dynamics in solution. While the anthracene dimer showed a fast V-shaped-to-planar conformational change within 10 ps in the lowest excited singlet state, reminding us of extended Baird aromaticity, the tetracene dimer and the pentacene dimer underwent intramolecular singlet fission (SF) in different manners: A fast and reversible SF with a characteristic delayed fluorescence (FL), and a fast and quantitative SF, respectively. Conformational flexibility of the fused COT linkage plays an important role in these ultrafast dynamics, demonstrating the utility of the flapping molecular series as a versatile platform for designing photofunctional systems.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| ange201802185-sup-0001-misc_information.pdf7.8 MB | Supplementary |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1
- 1aD. Shukla, P. Wan, J. Am. Chem. Soc. 1993, 115, 2990–2991;
- 1bC. Yuan, S. Saito, C. Camacho, S. Irle, I. Hisaki, S. Yamaguchi, J. Am. Chem. Soc. 2013, 135, 8842–8845;
- 1cC. Yuan, S. Saito, C. Camacho, T. Kowalczyk, S. Irle, S. Yamaguchi, Chem. Eur. J. 2014, 20, 2193–2200;
- 1dZ. Zhang, Y. Wu, K. Tang, C. Chen, J. Ho, J. Su, H. Tian, P. Chou, J. Am. Chem. Soc. 2015, 137, 8509–8520;
- 1eJ. Chen, Y. Wu, X. Wang, Z. Yu, H. Tian, J. Yao, H. Fu, Phys. Chem. Chem. Phys. 2015, 17, 27658–27664;
- 1fW. Chen, C. Chen, Z. Zhang, Y. Chen, W. Chao, J. Su, H. Tian, P. Chou, J. Am. Chem. Soc. 2017, 139, 1636–1644.
- 2
- 2aR. Kotani, H. Sotome, H. Okajima, S. Yokoyama, Y. Nakaike, A. Kashiwagi, C. Mori, Y. Nakada, S. Yamaguchi, A. Osuka, A. Sakamoto, H. Miyasaka, S. Saito, J. Mater. Chem. C 2017, 5, 5248–5256;
- 2bM. Hada, S. Saito, S. Tanaka, R. Sato, M. Yoshimura, K. Mouri, K. Matsuo, S. Yamaguchi, M. Hara, Y. Hayashi, F. Röhricht, R. Herges, Y. Shigeta, K. Onda, R. J. D. Miller, J. Am. Chem. Soc. 2017, 139, 15792–15800;
- 2cS. Saito, S. Nobusue, E. Tsuzaka, C. Yuan, C. Mori, M. Hara, T. Seki, C. Camacho, S. Irle, S. Yamaguchi, Nat. Commun. 2016, 7, 12094.
- 3
- 3aN. C. Baird, J. Am. Chem. Soc. 1972, 94, 4941–4948;
- 3bH. Ottosson, Nat. Chem. 2012, 4, 969–971;
- 3cM. Rosenberg, C. Dahlstrand, K. Kilså, H. Ottosson, Chem. Rev. 2014, 114, 5379–5425;
- 3dY. M. Sung, M.-C. Yoon, J. M. Lim, H. Rath, K. Naoda, A. Osuka, D. Kim, Nat. Chem. 2015, 7, 418–422;
- 3eH. Ottosson, Nat. Chem. 2015, 7, 373–375;
- 3fY. M. Sung, J. Oh, K. Naoda, T. Lee, W. Kim, M. Lim, A. Osuka, D. Kim, Angew. Chem. Int. Ed. 2016, 55, 11930–11934; Angew. Chem. 2016, 128, 12109–12113;
- 3gY. Hong, J. Oh, Y. M. Sung, Y. Tanaka, A. Osuka, D. Kim, Angew. Chem. Int. Ed. 2017, 56, 2932–2936; Angew. Chem. 2017, 129, 2978–2982;
- 3hM. Ueda, K. Jorner, Y. M. Sung, T. Mori, Q. Xiao, D. Kim, H. Ottosson, T. Aida, Y. Itoh, Nat. Commun. 2017, 8, 346;
- 3iJ. Oh, Y. M. Sung, H. Mori, S. Park, K. Jorner, H. Ottosson, M. Lim, A. Osuka, D. Kim, Chem 2017, 3, 870–880.
- 4S. Singh, W. J. Jones, W. Siebrand, B. P. Stoicheff, W. G. Schneider, J. Chem. Phys. 1965, 42, 330–342.
- 5General reviews on SF:
- 5aM. B. Smith, J. Michl, Chem. Rev. 2010, 110, 6891–6936;
- 5bM. B. Smith, J. Michl, Annu. Rev. Phys. Chem. 2013, 64, 361–386.
- 6First proposal and recent reviews on SF for enhancing photovoltaics efficiency:
- 6aM. C. Hanna, A. J. Nozik, J. Appl. Phys. 2006, 100, 074510;
- 6bJ. Xia, S. N. Sanders, W. Cheng, J. Z. Low, J. Liu, L. M. Campos, T. Sun, Adv. Mater. 2017, 29, 1601652;
- 6cA. Rao, R. H. Friend, Nat. Rev. Mater. 2017, 2, 17063.
- 7
- 7aA. M. Müller, Y. S. Avlasevich, K. Müllen, C. J. Bardeen, Chem. Phys. Lett. 2006, 421, 518–522;
- 7bA. M. Müller, Y. S. Avlasevich, W. W. Schoeller, K. Müllen, C. J. Bardeen, J. Am. Chem. Soc. 2007, 129, 14240–14250;
- 7cN. V. Korovina, S. Das, Z. Nett, X. Feng, J. Joy, R. Haiges, A. I. Krylov, S. E. Bradforth, M. E. Thompson, J. Am. Chem. Soc. 2016, 138, 617–627;
- 7dJ. D. Cook, T. J. Carey, N. H. Damrauer, J. Phys. Chem. A 2016, 120, 4473–4481;
- 7eH. Liu, R. Wang, L. Shen, Y. Xu, M. Xiao, C. Zhang, X. Li, Org. Lett. 2017, 19, 580–583;
- 7fJ. D. Cook, T. J. Carey, D. H. Arias, J. C. Johnson, N. H. Damrauer, J. Phys. Chem. A 2017, 121, 9229–9242;
- 7gT. J. Carey, E. G. Miller, A. T. Gilligan, T. Sammakia, N. H. Damrauer, Org. Lett. 2018, 20, 457–460.
- 8
- 8aJ. Zirzlmeier, D. Lehnherr, P. B. Coto, E. T. Chernick, R. Casillas, B. S. Basel, M. Thoss, R. R. Tykwinski, D. M. Guldi, Proc. Natl. Acad. Sci. USA 2015, 112, 5325–5330;
- 8bS. N. Sanders, E. Kumarasamy, A. B. Pun, M. T. Trinh, B. Choi, J. Xia, E. J. Taffet, J. Z. Low, J. R. Miller, X. Roy, X. Zhu, M. L. Steigerwald, M. Y. Sfeir, L. M. Campos, J. Am. Chem. Soc. 2015, 137, 8965–8972;
- 8cE. G. Fuemmeler, S. N. Sanders, A. B. Pun, E. Kumarasamy, T. Zeng, K. Miyata, M. L. Steigerwald, X.-Y. Zhu, M. Y. Sfeir, L. M. Campos, N. Ananth, ACS Cent. Sci. 2016, 2, 316–324;
- 8dS. Lukman, A. J. Musser, K. Chen, S. Athanasopoulos, C. K. Yong, Z. Zeng, Q. Ye, C. Chi, J. M. Hodgkiss, J. Wu, R. H. Friend, N. C. Greenham, Adv. Funct. Mater. 2015, 25, 5452–5461;
- 8eS. Lukman, K. Chen, J. M. Hodgkiss, D. H. P. Turban, N. D. M. Hine, S. Dong, J. Wu, N. C. Greenham, A. J. Musser, Nat. Commun. 2016, 7, 13622;
- 8fJ. Zirzlmeier, R. Casillas, S. R. Reddy, P. B. Coto, D. Lehnherr, E. T. Chernick, I. Papadopoulos, M. Thoss, R. R. Tykwinski, D. M. Guldi, Nanoscale 2016, 8, 10113;
- 8gT. Sakuma, H. Sakai, Y. Araki, T. Mori, T. Wada, N. V. Tkachenko, T. Hasobe, J. Phys. Chem. A 2016, 120, 1867–1875;
- 8hM. J. Y. Tayebjee, S. N. Sanders, E. Kumarasamy, L. M. Campos, M. Y. Sfeir, D. R. McCamey, Nat. Phys. 2017, 13, 182–188;
- 8iB. S. Basel, J. Zirzlmeier, C. Hetzer, B. T. Phelan, M. D. Krzyaniak, S. R. Reddy, P. B. Coto, N. H. Horwitz, R. M. Young, F. J. White, F. Hampel, T. Clark, M. Thoss, R. R. Tykwinski, M. R. Wasielewski, D. M. Guldi, Nat. Commun. 2017, 8, 15171;
- 8jM. T. Trinh, A. Pinkard, A. B. Pun, S. N. Sanders, E. Kumarasamy, M. Y. Sfeir, L. M. Campos, X. Roy, X.-Y. Zhu, Sci. Adv. 2017, 3, e 1700241;
- 8kE. Kumarasamy, S. N. Sanders, M. J. Y. Tayebjee, A. Asadpoordarvish, T. J. H. Hele, E. G. Fuemmeler, A. B. Pun, L. M. Yablon, J. Z. Low, D. W. Paley, J. C. Dean, B. Choi, G. D. Sholes, M. L. Steigerwald, N. Ananth, D. R. McCamey, M. Y. Sfeir, L. M. Campos, J. Am. Chem. Soc. 2017, 139, 12488–12494;
- 8lE. Garoni, J. Zirzlmeier, B. S. Basel, C. Hetzer, K. Kamada, D. M. Guldi, R. R. Tykwinski, J. Am. Chem. Soc. 2017, 139, 14017–14020.
- 9
- 9aJ. C. Johnson, A. Akdag, M. Zamadar, X. Chen, A. F. Schwerin, I. Paci, M. B. Smith, Z. Havlas, J. R. Miller, M. A. Ratner, A. J. Nozik, J. Michl, J. Phys. Chem. B 2013, 117, 4680–4695;
- 9bE. A. Margulies, C. E. Miller, Y. Wu, L. Ma, G. C. Schatz, R. M. Young, M. R. Wasielewski, Nat. Chem. 2016, 8, 1120–1125;
- 9cY. Wu, Y. Wang, J. Chen, G. Zhang, J. Yao, D. Zhang, H. Fu, Angew. Chem. Int. Ed. 2017, 56, 9400–9404; Angew. Chem. 2017, 129, 9528–9532;
- 9dJ. C. Dean, R. Zhang, R. K. Hallani, R. D. Pensack, S. N. Sanders, D. G. Oblinsky, S. R. Parkin, L. M. Campos, J. E. Anthony, G. D. Scholes, Phys. Chem. Chem. Phys. 2017, 19, 23162–23175;
- 9eR. Montero, V. Martínez-Martínez, A. Longarte, N. Epelde-Elezcano, E. Palao, I. Lamas, H. Manzano, A. R. Agarrabeitia, I. L. Arbeloa, M. J. Ortiz, I. Garcia-Moreno, J. Phys. Chem. Lett. 2018, 9, 641–646.
- 10
- 10aP. A. Wender, J. P. Christy, J. Am. Chem. Soc. 2007, 129, 13402–13403;
- 10bP. A. Wender, A. B. Lesser, L. E. Sirois, Angew. Chem. Int. Ed. 2012, 51, 2736–2740; Angew. Chem. 2012, 124, 2790–2794.
- 11
- 11aJ. E. Anthony, D. L. Eaton, S. R. Parkin, Org. Lett. 2002, 4, 15–18;
- 11bW. Fudickar, T. Linker, J. Am. Chem. Soc. 2012, 134, 15071–15082.
- 12M. J. Y. Tayebjee, A. Mahboubi Soufiani, G. J. Conibeer, J. Phys. Chem. C 2014, 118, 2298–2305.
- 13J. J. Snellenburg, S. P. Laptenok, R. Seger, K. M. Mullen, I. H. M. van Stokkum, J. Stat. Soft. 2012, 49, 1–22.
- 14
- 14aP. J. Vallett, J. L. Snyder, N. H. Damrauer, J. Phys. Chem. A 2013, 117, 10824–10838;
- 14bE. C. Alguire, J. E. Subotnik, N. H. Damrauer, J. Phys. Chem. A 2015, 119, 299–311;
- 14cK. Miyata, Y, Kurashige, K. Watanabe, T. Sugimoto, S. Takahashi, S. Tanaka, J. Takeya, T. Yanai, Y. Matsumoto, Nat. Chem. 2017, 9, 983–989.
- 15R. Ayub, O. E. Bakouri, K. Jorner, M. Solà, H. Ottosson, J. Org. Chem. 2017, 82, 6327–6340.
- 16
- 16aP. G. Szalay, T. Müller, G. Gidofalvi, H. Lischka, R. Shepard, Chem. Rev. 2012, 112, 108–181;
- 16bD. I. Lyakh, M. Musiał, V. F. Lotrich, R. J. Bartlett, Chem. Rev. 2012, 112, 182–243.
- 17
- 17aM. K. Beyer, H. Clausen-Schaumann, Chem. Rev. 2005, 105, 2921–2948;
- 17bM. M. Caruso, D. A. Davis, Q. Shen, S. A. Odom, N. R. Sottos, S. R. White, J. S. Moore, Chem. Rev. 2009, 109, 5755–5798;
- 17cA. L. Black, J. M. Lenhardt, S. L. Craig, J. Mater. Chem. 2011, 21, 1655–1663;
- 17dJ. Li, C. Nagamani, J. S. Moore, Acc. Chem. Res. 2015, 48, 2181–2190.
- 18
- 18aW. Grochala, R. Hoffmann, J. Feng, N. W. Ashcroft, Angew. Chem. Int. Ed. 2007, 46, 3620–3642; Angew. Chem. 2007, 119, 3694–3717;
- 18bR. Lee, J. A. K. Howard, M. R. Probert, J. W. Steed, Chem. Soc. Rev. 2014, 43, 4300–4311;
- 18cY. Dong, B. Xu, J. Zhang, X. Tan, L. Wang, J. Chen, H. Lv, S. Wen, B. Li, L. Ye, B. Zou, W. Tian, Angew. Chem. Int. Ed. 2012, 51, 10782–10785; Angew. Chem. 2012, 124, 10940–10943;
- 18dK. Nagura, S. Saito, H. Yusa, H. Yamawaki, H. Fujihisa, H. Sato, Y. Shimoikeda, S. Yamaguchi, J. Am. Chem. Soc. 2013, 135, 10322–10325.
- 19CCDC 1822727, 1822728, and 1822729 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
Citing Literature
This is the
German version
of Angewandte Chemie.
Note for articles published since 1962:
Do not cite this version alone.
Take me to the International Edition version with citable page numbers, DOI, and citation export.
We apologize for the inconvenience.
