Corral[<i>n</i>]Bicarbazoles: Redox‐Active Chiral Macrocycles for Air‐Stable Radical Cations Formation and Guest Capture/Release
Abstract
AbstractMacrocyclic compounds are pivotal in both supramolecular chemistry and materials science, as their preorganized cavities enable selective molecular recognition, while their cyclic frameworks facilitate electronic and spatial coupling of monomeric units to yield advanced optoelectronic and magnetic properties. However, macrocycles that combine exceptional host–guest recognition with these properties remain rare and challenging to design. Herein, we report the synthesis of three pairs of enantiopure, redox‐active, conjugated macrocycles, termed corral[n]bicarbazole, employing axially chiral 4,4′‐bicarbazole units. These macrocycles display strong blue emission (quantum yields up to 78% in THF) and pronounced circularly polarized luminescence (|glum| up to 10−3). Notably, controlled oxidation of corral[n]bicarbazoles generates their mono‐ and polyradical cations with exceptional air stability (half‐lives up to five days) and intriguing magnetic properties. The electron‐rich deep‐cavity of corral[4]bicarbazole confers strong hosting ability (Ka = 104–105 M−1) toward cationic guests, facilitating redox‐responsive guest capture/release. By integrating a chiroptical, redox‐active backbone with a switchable recognition cavity, corral[n]bicarbazoles offer a versatile platform for advancing interdisciplinary innovation, with potential applications in optoelectronics, spintronics, and smart supramolecular materials.
Article Details
Authors (10)
Ruiguo Wang
Han Han
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
Li‐Bo Jing
College of Chemistry State Key Laboratory of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter Nankai University Tianjin 300071 China
Peng‐Yao Shen
College of Chemistry State Key Laboratory of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter Nankai University Tianjin 300071 China
Xiao Xiao
The Education Ministry Key Lab of Resource Chemistry, Shanghai Frontiers Science Center of Biomimetic Catalysis
Jia‐Ying Deng
College of Chemistry State Key Laboratory of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter Nankai University Tianjin 300071 China
Qi Zhang
Haiting Di
College of Chemistry State Key Laboratory of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter Nankai University Tianjin 300071 China
Dong‐Sheng Guo
College of Chemistry, State Key Laboratory of Medicinal Chemical Biology Key Laboratory of Functional Polymer Materials (Ministry of Education) Frontiers Science Center For New Organic Matter Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) Nankai University Tianjin China
Kang Cai
College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, 94 Weijin Road, Nankai District, Tianjin 300071, China