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- Title
Symmetry-breaking host–guest assembly in a hydrogen-bonded supramolecular system.
- Authors
Horiuchi, Shinnosuke; Yamaguchi, Takumi; Tessarolo, Jacopo; Tanaka, Hirotaka; Sakuda, Eri; Arikawa, Yasuhiro; Meggers, Eric; Clever, Guido H.; Umakoshi, Keisuke
- Abstract
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 C1-symmetric supramolecular structure from an Oh-symmetric hydrogen-bonded resorcin[4]arene capsule and C2-symmetric cationic bis-cyclometalated Ir complexes, carrying sterically demanding tertiary butyl (tBu) 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 (glum) in the circularly polarized luminescence. Self-assembly processes usually yield symmetric compounds. Here, the authors report the distortion of a symmetric hydrogen-bonded resorcin[4]arene cage upon encapsulation of an iridium complex.
- Subjects
RESORCINOL; MAGNETIC dipoles; EXCITED states; IRIDIUM; LUMINESCENCE
- Publication
Nature Communications, 2023, Vol 14, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-023-35850-4