Abstract
Binding of fluorescent molecules to the porous matrix through noncovalent interactions will synergistically expand their application spectrum. In this regard, we report an integrative self-assembly of molecule 1 with benzothiadizole and 9,9-dihexyl fluorene units, and covalent organic frameworks (COFs) via an emulsion-modulated polymerization process, within which molecules of 1 are able to interact with the scaffolds of COFs through CH-π interactions. Thus the π-π interactions between the fluorescent molecules are largely suppressed, giving rise to their remarkable monomer-like optical properties. Of particular interest is that, given by the specific interaction between COFs and a nerve agent simulant diethyl chlorophosphite (DCP), these assembled composites show the ability of ultrasensitive detection of DCP with a detection limit of ∼40 ppb. Moreover, the present integrative assembly strategy can be extended to encapsulate multiple fluorescent molecules, enabling the assemblies with white light emission. Our results highlight opportunities for the development of highly emissive porous materials by molecular self-assembly of fluorophores and molecular units of COFs.
摘要
荧光分子通过非共价键作用载入到多孔矩阵中能够拓展其 应用范围. 本文报道了利用乳液限域的方法将带有苯并噻二唑和 9,9-二己基芴基团的荧光分子1和共价有机框架(Covalent Organic Frameworks, COFs)一体化自组装, 使得分子1通过CH-π作用固定 在共价有机框架的骨架之上. 因此这会极大地抑制荧光分子之间 的π-π作用, 使其表现出荧光分子单体的光学性质. 更有意思的是, 共价有机框架和神经毒剂模拟物(DCP)的特殊的作用, 使得一体化 自组装的复合物能够实现对神经毒剂模拟物高灵敏度的检测(检测 限为40 ppb). 而且, 当前的一体化组装策略能够被拓展用于装载多 种不同发射波长的荧光分子来实现白光. 我们的结果提供了一种 利用荧光探针分子和共价有机框架综合自组装来制备高发光效率 多孔材料的新方法.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21703120, 21972076, 51903140 and 21925604), China Postdoctoral Science Foundation (2019M662324), and Taishan Scholars Program of Shandong Province (tsqn201812011).
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Yang Z designed and engineered the samples; Gong Y, Guo Y, Qiu C, Zhang Z, Zhang F, Wei Y and Wang S performed the experiments; Che Y, Wei J and Yang Z wrote the paper. All authors contributed to the general discussion.
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Experimental details and supporting data are available in the online version of the paper.
Yanke Che is currently a professor at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS). He received a bachelor degree from Xi’an Jiaotong University and completed PhD at ICCAS. His research covers a broad range in nanomaterials, nanoscale and molecular imaging and probing, optoelectronic sensors and nanodevices, aiming at long-term real applications in the fields relevant to environment.
Jingjing Wei is a professor at the School of Chemistry and Chemical Engineering, Shandong University. She got a BSc degree in chemistry from Shandong Normal University and a PhD degree from Sorbonne University in Paris. After two years of postdoctoral training in Sorbonne University and the Institute for Basic Science of South Korea, she was appointed a faculty member in Shandong University. Her current research interests are organic porous materials and their applications.
Zhijie Yang is a professor at the School of Chemistry and Chemical Engineering, Shandong University. He holds a BSc degree in chemistry from Shandong University and a PhD degree in physical chemistry from Sorbonne University, France. Before he was appointed a faculty member, he did his postdoctoral research at the Center for Soft and Living Matter, Institute for Basic Science, Korea. His current research interests are self-assembly of nanoscaled materials for their emerging applications.
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Gong, Y., Guo, Y., Qiu, C. et al. Integrative self-assembly of covalent organic frameworks and fluorescent molecules for ultrasensitive detection of a nerve agent simulant. Sci. China Mater. 64, 1189–1196 (2021). https://doi.org/10.1007/s40843-020-1517-8
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DOI: https://doi.org/10.1007/s40843-020-1517-8