Macrocycle‐Based Crystalline Sponge that Stabilizes and Lights Up Cationic Aggregation‐Caused Quenching Dyes
Macrocycle‐Based Crystalline Sponge that Stabilizes and Lights Up Cationic Aggregation‐Caused Quenching Dyes
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DOI：
10.1002/adom.202101670
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发表时间：
2021-10
影响因子：
9
通讯作者：
Xin Sun;Yu-Dong Yang;Xu-Lang Chen;Ai-Huan Sun;Jun-feng Xiang;H. Gong
中科院分区：
文献类型：
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作者：
Xin Sun;Yu-Dong Yang;Xu-Lang Chen;Ai-Huan Sun;Jun-feng Xiang;H. Gong
固态荧光材料在发光二极管、激光染料、存储材料和荧光传感器的制造中发挥着关键作用。然而，使用传统的有机染料生产固态荧光材料仍然具有挑战性，因为大多数染料在固态时都会受到聚集引起的猝灭(ACQ)。在这里，大环衍生的晶体框架被报道，捕捉各种阳离子测试-ACQ染料(例如，碱性红2(BR2))并以荧光的形式稳定它们。Cyclo[3](1，3‐benzene)[3](4，6‐benzene)(1，3‐dicarboxylic酸)，CA-3，作为核心大环构筑块。当允许与锌(NO_3)_2·6H_2O或镉(NO_3)_2·4H_2O配位时，得到结晶海绵(CS-Zn或CS-Cd)。在CS-Zn的情况下，在固体中观察到纳米尺寸的空腔作为容器来捕获阳离子ACQ染料BR2，负载率高达14.6wt%，发射增强高达固体BR2的41倍。得到的含染料材料CS-Zn@Br2在室温或回流条件下，或在300°C的空气中加热1小时，或在次氯酸钠溶液(3.0 mm)存在下，在水或选定的有机溶剂中表现出高度的稳定性。这项研究强调了一种在固体中呈现荧光ACQ染料的新策略。
Solid‐state fluorescent materials play a critical role in the manufacture of light‐emitting diodes, laser dyes, storage materials, and fluorescence sensors. However, it remains challenging to produce solid‐state fluorescent materials using traditional organic dyes since most are subject to aggregation‐caused quenching (ACQ) in the solid state. Here, a macrocycle‐derived crystalline framework is reported that captures various cationic test‐ACQ dyes (e.g., Basic Red 2 (BR2)) and stabilizes them in a fluorescent form. Cyclo[3](1,3‐benzene)[3](4,6‐benzene)(1,3‐dicarboxylic acid), CA‐3, is used as the core macrocyclic building block. When allowed to coordinate with Zn(NO3)2•6H2O or Cd(NO3)2•4H2O, crystalline sponge (CS‐Zn or CS‐Cd) is obtained. In the case of CS‐Zn, nano‐sized cavities are observed in the solid state that serve as containers to capture the cationic ACQ dye BR2 with loading yields up to 14.6 wt% and emission enhancements up to 41× of those seen for solid BR2. The resulting dye‐containing material, CS‐Zn@BR2, displays high stability in water or selected organic solvents at room temperature or under reflux, or when heated at 300 °C for 1 h open to the air, or in the presence of sodium hypochlorite solution (3.0 mm). This study highlights a new strategy for rendering fluorescent ACQ dyes in the solid state.