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

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Sep 24

PMID 39315432

Authors

Reiji Yoshina

Junichiro Hirano

Emiko Nishimoto

Yuki Sakamoto

Keita Tajima

Shunsuke Minabe

Muhammet Uyanik

Kazuaki Ishihara

Tomoyuki Ikai

Eiji Yashima

Takuya Omine

Fumitaka Ishiwari

Akinori Saeki

Jinseok Kim

Juwon Oh

Dongho Kim

Guanting Liu

Takuma Yasuda

Hiroshi Shinokubo

Norihito Fukui

Affiliations

Soon will be listed here.

Abstract

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral -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[,]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 value of 1.0 × 10. This 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.

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