Symmetry-breaking host-guest assembly in a hydrogen-bonded supramolecular system.

Autor: Horiuchi S; Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521, Japan. shoriuchi@g.ecc.u-tokyo.ac.jp.; Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227, Dortmund, Germany. shoriuchi@g.ecc.u-tokyo.ac.jp.; Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo, 153-8902, Japan. shoriuchi@g.ecc.u-tokyo.ac.jp., Yamaguchi T; School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, 923-1292, Japan., Tessarolo J; Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227, Dortmund, Germany., Tanaka H; Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521, Japan., Sakuda E; Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521, Japan.; Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227, Dortmund, Germany., Arikawa Y; Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521, Japan., Meggers E; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Clever GH; Department of Chemistry and Chemical Biology, TU Dortmund University, Otto-Hahn-Straße 6, 44227, Dortmund, Germany. guido.clever@tu-dortmund.de., Umakoshi K; Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521, Japan. kumks@nagasaki-u.ac.jp.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2023 Jan 11; Vol. 14 (1), pp. 155. Date of Electronic Publication: 2023 Jan 11.
DOI: 10.1038/s41467-023-35850-4
Abstrakt: Bio-inspired self-assembly is invaluable to create well-defined giant structures from small molecular units. Owing to a large entropy loss in the self-assembly process, highly symmetric structures are typically obtained as thermodynamic products while formation of low symmetric assemblies is still challenging. In this study, we report the symmetry-breaking self-assembly of a defined C 1 -symmetric supramolecular structure from an O h -symmetric hydrogen-bonded resorcin[4]arene capsule and C 2 -symmetric cationic bis-cyclometalated Ir complexes, carrying sterically demanding tertiary butyl ( t Bu) groups, on the basis of synergistic effects of weak binding forces. The flexible capsule framework shows a large structural change upon guest binding to form a distorted resorcin[4]arene hexameric capsule, providing an asymmetric cavity. Location of the chiral guest inside the anisotropic environment leads to modulation of its Electric Dipole (ED) and Magnetic Dipole (MD) transition moments in the excited state, causing an increased emission quantum yield, longer emission lifetime, and enhancement of the dissymmetry factor (g lum ) in the circularly polarized luminescence.
(© 2023. The Author(s).)
Databáze: MEDLINE
Externí odkaz: