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Manipulations of Chiroptical Properties in Belt‐Persistent Cycloarylenes via Desymmetrization with Heteroatom Doping
Author(s) -
Fukunaga Toshiya M.,
Sawabe Chizuru,
Matsuno Taisuke,
Takeya Jun,
Okamoto Toshihiro,
Isobe Hiroyuki
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202106992
Subject(s) - desymmetrization , dipole , heteroatom , transition dipole moment , moment (physics) , doping , coupling (piping) , chemistry , electric dipole moment , chemical physics , materials science , computational chemistry , stereochemistry , physics , optoelectronics , organic chemistry , enantioselective synthesis , ring (chemistry) , quantum mechanics , composite material , catalysis
A desymmetrization strategy has been devised in the design of molecular cylinders to maximize the dissymmetry factor relevant to circularly polarized light. Although the highest dissymmetry factor of organic molecules was previously achieved with a chiral belt‐persistent cycloarylene having magnetic and electric transition dipole moments in parallel, we noticed that an unbalanced magnitude of two moments was detrimental for higher dissymmetry factors. In this study, a molecular cylinder was desymmetrized by arraying doped and undoped panels via stereoselective cross‐coupling macrocyclization. The desymmetrization succeeded in balancing two moments by reducing the electric transition moment at the global minimum but failed to maximize the dissymmetry factor. Structural studies revealed that the dissymmetry factor is sensitive to subtle structural fluctuations, while the rotatory strength is not affected. This study is important for the development of chiroptical materials.