Circularly Polarized Luminescence in Chiral π‐Conjugated Macrocycles

Hasegawa, Masashi; Nojima, Yuki; Mazaki, Yasuhiro

doi:10.1002/cptc.202100162

Cited by 104 publications

(103 citation statements)

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“… 45 Indeed, in comparison to other small organic molecules in solution, the circularly polarized luminescence of 1 is the most red-shifted and has one of the highest dissymmetry factors ( Table S3 ). 50 − 53 The PDI electron-accepting ability of 1 is also elevated (Δ E 1/2 = 0.1 V) and matches that of a tetrachloro-substituted PDI semiconducting material 34 but with a notably higher barrier to stereoisomer interconversion (Δ G ‡ = 108 vs 97 kJ mol –1 ). 33 Therefore, this work demonstrates that the ordering of dynamic chiral PDIs using macrocyclic scaffolds can elevate their key chiroptical and electrochemical properties.…”

Section: Discussionmentioning

confidence: 63%

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

et al. 2022

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This work showcases chiral complementarity in aromatic stacking interactions as an effective tool to optimize the chiroptical and electrochemical properties of perylene diimides (PDIs). PDIs are a notable class of robust dye molecules and their rich photo- and electrochemistry and potential chirality make them ideal organic building blocks for chiral optoelectronic materials. By exploiting the new bay connectivity of twisted PDIs, a dynamic bis-PDI macrocycle (the “Pink Box”) is realized in which homochiral PDI–PDI π–π stacking interactions are switched on exclusively. Using a range of experimental and computational techniques, we uncover three important implications of the macrocycle’s chiral complementarity for PDI optoelectronics. First, the homochiral intramolecular π–π interactions anchor the twisted PDI units, yielding enantiomers with half-lives extended over 400-fold, from minutes to days (in solution) or years (in the solid state). Second, homochiral H-type aggregation affords the macrocycle red-shifted circularly polarized luminescence and one of the highest dissymmetry factors of any small organic molecule in solution ( g lum = 10 –2 at 675 nm). Finally, excellent through-space PDI–PDI π-orbital overlap stabilizes PDI reduced states, akin to covalent functionalization with electron-withdrawing groups.

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Section: Discussionmentioning

confidence: 63%

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

et al. 2022

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“…283 Thus, luminescent cyclophanes bearing point, axial, planar, or helical chirality arise as relevant CPL emitters. 284…”

Section: Applicationsmentioning

confidence: 99%

Fluorescent cyclophanes and their applications

et al. 2022

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“…In recent years, helicene‐based materials have shown great potential in the field of chiral optoelectronic devices, for which significant chiroptical responses in the visible region with high dissymmetry factors are desirable. [ 43 ] Up to date, only very few helicenes exhibit dissymmetry factors up to 10 −2 in the visible region, calling for new designs of helicene‐based chiroptical materials. In 2021, Wang and co‐workers reported the synthesis and chiroptical properties of N,B,N‐type 1,4‐azaborine‐embedded double [7]helicenes 69 ( Figure 4 a ).…”

Section: The Value Of Incorporating 14‐azaborinesmentioning

confidence: 99%

The Rise of 1,4‐BN‐Heteroarenes: Synthesis, Properties, and Applications

Chen

2022

Advanced Science

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Dedicated to Professor Klaus Müllen on the occasion of his 75th birthdayBN-heteroarenes, which employ both boron and nitrogen in aromatic hydrocarbons, have gained great attention in the fields of organic chemistry and materials science. Nevertheless, the extensive studies on BN-heteroarenes are largely limited to 1,2-azaborine-based compounds with B-N covalent bonds, whereas 1,3-and 1,4-BN-heteroarenes are relatively rare due to their greater challenge in the synthesis. Recently, significant progresses have been achieved in the synthesis and applications of BN-heteroarenes featuring 1,4-azaborines, especially driven by their significant potential as multiresonant thermally activated delayed fluorescence (MR-TADF) materials. Therefore, it is timely to review these advances from the chemistry perspective. This review summarizes the synthetic methods and recent achievements of 1,4-azaborine-based BN-heteroarenes and discusses their unique properties and potential applications of this emerging class of materials, highlighting the value of 1,4-BN-heteroarenes beyond MR-TADF materials. It is hoped that this review would stimulate the conversation and cooperation between chemists who are interested in azaborine chemistry and materials scientists working in the fields of organic optoelectronics, metal catalysis, and carbon-based nanoscience etc.

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Circularly Polarized Luminescence in Chiral π‐Conjugated Macrocycles

Cited by 104 publications

References 96 publications

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

The Pink Box: Exclusive Homochiral Aromatic Stacking in a Bis-perylene Diimide Macrocycle

Fluorescent cyclophanes and their applications

The Rise of 1,4‐BN‐Heteroarenes: Synthesis, Properties, and Applications

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