Self‐Assembly of Macrocyclic Triangles into Helicity‐Opposite Nanotwists by Competitive Planar over Point Chirality

• Published in: Angewandte Chemie Vol. 134; no. 41
• Main Authors: Shang, Weili, Zhu, Xuefeng, Jiang, Yuqian, Cui, Jie, Liu, Kaiang, Li, Tiesheng, Liu, Minghua
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 10.10.2022
• Subjects: Apexes; Assembly; Biomimetics; Chemistry; Chirality; Circularly Polarized Luminescence; Evolution; Graph theory; Handedness; Helicity; Macrocyclic Diastereomer; Nanotwist; Planar Chirality; Self-Assembly
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202210604

While helix has elegant biomimetic structures and functionalities, it still remains a big question how the nanoscale helicity evolved from the molecular chiral building blocks across length scales. Herein, macrocyclic triangles composed of achiral edges and chiral vertices were rationally designed, in which the planar chirality emerged due to the restriction of edge rotation by intermolecular stackings and led to a unique chiral self‐assembly. In contrast to the solution systems where the chiroptical property is exclusively dominated by the point chiral vertices, the emerged planar chirality was found to control the chiral self‐assembly, resulting the nanotwist with the handedness determined by the planar chirality. Our work unveiled the self‐assembly behaviors of macrocyclic conformers for the first time and provided a deep understanding on the macrocyclic chirality evolution including the excited‐state chirality. Planar chirality emerging from the restriction rotation of achiral edges in macrocyclic triangles containing chiral vertices has led to chiral self‐assembly. In contrast to solution systems, where chiroptical properties are exclusively dominated by the point chiral vertices, the emerging planar chirality arising from intermolecular stacking controls the chiral self‐assembly.