Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons.

Autor: Yoshina R; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Hirano J; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Nishimoto E; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Sakamoto Y; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Tajima K; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Minabe S; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Uyanik M; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Ishihara K; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Ikai T; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan.; PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan., Yashima E; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Omine T; Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan., Ishiwari F; PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan.; Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan., Saeki A; Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan., Kim J; Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 03722, Korea., Oh J; Department of Chemistry, Soonchunhyang University, Asan, Chungnam 31538, Republic of Korea., Kim D; Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 03722, Korea., Liu G; Institute for Advanced Study, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan., Yasuda T; Institute for Advanced Study, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan., Shinokubo H; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan., Fukui N; Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan.; PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Oct 30; Vol. 146 (43), pp. 29383-29390. Date of Electronic Publication: 2024 Sep 24.
DOI: 10.1021/jacs.4c07985
Abstrakt: Figure-eight-shaped nonplanar π-systems adopt distinctive chiral D 2 -symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., dibenzo[ g , p ]chrysene (DBC), catalytically affords a figure-eight electron-accepting macrocycle, i.e., cyclobisbiphenylenecarbonyl (CBBC), with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). This inner-bond-cleavage approach also applies to larger PAHs, affording highly distorted molecular frameworks that comprise two figure-eight subunits. Furthermore, we demonstrate that the peripheral functionalization of CBBC with carbazole afforded donor-acceptor-type emitter, which shows thermally activated delayed fluorescence and emits CPL with a g value of 1.0 × 10 -2 . This g value is ten times higher than those of previously reported chiral TADF-active emitters for circularly polarized organic light-emitting diodes. These results demonstrate that oxidative inner-bond cleavage is a powerful synthetic strategy for creating innovative materials that incorporate molecules with figure-eight structures.
Databáze: MEDLINE
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