Wang Ruiguo, Han Han, Jing Li-Bo, Shen Peng-Yao, Xiao Xiao, Deng Jia-Ying, Zhang Qi, Di Haiting, Guo Dong-Sheng, Cai Kang
College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, 300071, China.
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, SAR, 999077, China.
Angew Chem Int Ed Engl. 2025 Oct 6;64(41):e202511366. doi: 10.1002/anie.202511366. Epub 2025 Aug 22.
Macrocyclic 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 (|g| up to 10). 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 (K = 10-10 M) 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.
大环化合物在超分子化学和材料科学中都至关重要，因为它们预先形成的空腔能够实现选择性分子识别，而其环状骨架则有利于单体单元的电子和空间耦合，从而产生先进的光电和磁性。然而，将卓越的主客体识别与这些性质相结合的大环化合物仍然很少见，且设计颇具挑战性。在此，我们报道了使用轴向手性4,4'-联咔唑单元合成三对对映体纯的、具有氧化还原活性的共轭大环化合物，称为围场[n]联咔唑。这些大环化合物表现出强烈的蓝色发射（在四氢呋喃中的量子产率高达78%）和显著的圆偏振发光（|g|高达10）。值得注意的是，围场[n]联咔唑的可控氧化产生了它们的单自由基和多自由基阳离子，具有出色的空气稳定性（半衰期长达五天）和有趣的磁性。围场[4]联咔唑富含电子的深腔对阳离子客体具有很强的容纳能力（K = 10-10 M），有利于氧化还原响应的客体捕获/释放。通过将手性光学、氧化还原活性主链与可切换的识别腔相结合，围场[n]联咔唑为推进跨学科创新提供了一个多功能平台，在光电子学、自旋电子学和智能超分子材料方面具有潜在应用。
