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AIE-Driven Chiral Covalent Organic Frameworks for Solid-State Circularly Polarized Luminescence, Hydrochromism, and Water-Induced Chiroptical Enhancement
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2025-06-04 , DOI: 10.1002/anie.202509454
Mengjuan Zuo, Xinlin Zha, Zhenzhen Jiang, Mengying Luo, Zhong Yan, Haining You, Xing Qing, Yi Xiong, Ying Liu, Liu Liu, Yingying Li, Wen Wang, Mufang Li, Dong Wang
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2025-06-04 , DOI: 10.1002/anie.202509454
Mengjuan Zuo, Xinlin Zha, Zhenzhen Jiang, Mengying Luo, Zhong Yan, Haining You, Xing Qing, Yi Xiong, Ying Liu, Liu Liu, Yingying Li, Wen Wang, Mufang Li, Dong Wang
Chiral covalent organic frameworks (CCOFs) are promising candidates for chiral optoelectronics and sensing, but their weak solid-state fluorescence and chiroptical responses often limit practical utility. Here, we introduce a novel CCOF synthesized from achiral monomers, 2-hydroxy-1,3,5-benzenetricarbaldehyde and hydrazine, via imine condensation with chiral induction strategy, yielding salicylaldehyde azine units with aggregation-induced emission. Optimized catalyst and chiral inducer stoichiometry endow the framework with exceptional chiroptical properties (|gabs| = 2.2 × 10-2, ellipticity ≈ 1000 mdeg). In the solid state, the CCOF exhibits intense red fluorescence (λem ≈ 645 nm) and favorable circularly polarized luminescence (CPL, |glum| = 5.2 × 10-2), marking the first CCOF derived solely from achiral building blocks with robust solid-state CPL. When integrated into polydimethylsiloxane, it forms flexible and semitransparent composite films suitable for CPL-based applications. The CCOF also functions as highly enantioselective fluorescent sensors for chiral analytes, including 2-aminocyclohenanol and dimethyl-1,2-cyclohexanediamine. Furthermore, it demonstrates reversible hydrochromism, transitioning from yellow to orange (ΔE ≈ 42.7), and water-induced chiroptical enhancement (ellipticity up to 2100 medg, |gabs| = 5.5 × 10-2), achieving the highest ground-state chirality reported for CCOFs through enol-to-keto tautomerism upon water adsorption. This stimulus-responsive CCOF with solid-state CPL properties provides new insights into chiral functional materials.
中文翻译:
AIE 驱动的手性共价有机框架,用于固态圆偏振发光、水变色和水诱导手性增强
手性共价有机框架 (CCOF) 是手性光电子学和传感的有前途的候选者,但它们较弱的固态荧光和手光反应通常会限制实际实用性。在这里,我们介绍了一种由非手性单体、2-羟基-1,3,5-苯三甲醛和肼合成的新型 CCOF,通过手性诱导策略的亚胺缩合,产生具有聚集诱导发射的水杨醛嗪单元。优化的催化剂和手性诱导剂化学计量学赋予该框架卓越的手性特性 (|gabs| = 2.2 × 10-2,椭圆度 ≈ 1000 mdeg)。在固态下,CCOF 表现出强烈的红色荧光 (λem ≈ 645 nm) 和有利的圆偏振发光 (CPL, |glum| = 5.2 × 10-2),标志着第一个仅源自具有稳健固态 CPL 的非手性结构单元的 CCOF。当集成到聚二甲基硅氧烷中时,它会形成柔性和半透明复合膜,适用于基于 CPL 的应用。CCOF 还可用作手性分析物(包括 2-氨基环海宁和二甲基-1,2-环己二胺)的高对映选择性荧光传感器。此外,它表现出可逆的水变色作用,从黄色转变为橙色 (ΔE ≈ 42.7) 和水诱导的手性增强(椭圆度高达 2100 medg,|gabs| = 5.5 × 10-2),通过水吸附时的烯醇-酮互变异构实现了 CCOF 报道的最高基态手性。这种具有固态 CPL 特性的刺激响应 CCOF 为手性功能材料提供了新的见解。
更新日期:2025-06-04
中文翻译:

AIE 驱动的手性共价有机框架,用于固态圆偏振发光、水变色和水诱导手性增强
手性共价有机框架 (CCOF) 是手性光电子学和传感的有前途的候选者,但它们较弱的固态荧光和手光反应通常会限制实际实用性。在这里,我们介绍了一种由非手性单体、2-羟基-1,3,5-苯三甲醛和肼合成的新型 CCOF,通过手性诱导策略的亚胺缩合,产生具有聚集诱导发射的水杨醛嗪单元。优化的催化剂和手性诱导剂化学计量学赋予该框架卓越的手性特性 (|gabs| = 2.2 × 10-2,椭圆度 ≈ 1000 mdeg)。在固态下,CCOF 表现出强烈的红色荧光 (λem ≈ 645 nm) 和有利的圆偏振发光 (CPL, |glum| = 5.2 × 10-2),标志着第一个仅源自具有稳健固态 CPL 的非手性结构单元的 CCOF。当集成到聚二甲基硅氧烷中时,它会形成柔性和半透明复合膜,适用于基于 CPL 的应用。CCOF 还可用作手性分析物(包括 2-氨基环海宁和二甲基-1,2-环己二胺)的高对映选择性荧光传感器。此外,它表现出可逆的水变色作用,从黄色转变为橙色 (ΔE ≈ 42.7) 和水诱导的手性增强(椭圆度高达 2100 medg,|gabs| = 5.5 × 10-2),通过水吸附时的烯醇-酮互变异构实现了 CCOF 报道的最高基态手性。这种具有固态 CPL 特性的刺激响应 CCOF 为手性功能材料提供了新的见解。