Lin Zu-Jin, Qin Jin-Ying, Zhan Xiao-Ping, Wu KeChen, Cao Gao-Juan, Chen Banglin
College of Life Science, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002, P. R. China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
ACS Appl Mater Interfaces. 2022 May 11;14(18):21098-21105. doi: 10.1021/acsami.2c05176. Epub 2022 Apr 28.
Although tremendous progress has been achieved in the field of hydrogen-bonded organic frameworks (HOFs), the low stability, small/none pores, and difficult functionality severely obstruct their development. Herein, a novel robust mesoporous HOF (HOF-FAFU-1) decorated with a high density of free hydroxy moieties has been designed and readily synthesized in the synthesis. In HOF-FAFU-1, the planar building blocks are connected to each other by typical intermolecular carboxylate dimers to form two-dimensional (2D) layers with topology, which are further connected to their adjacent layers by face-to-face π-π interactions to obtain a three-dimensional (3D) open mesoporous framework. Owing to the high density of intermolecular hydrogen bonding and strong π-π interactions, HOF-FAFU-1 is very stable, allowing it to retain its structure in aqueous solutions with a pH range of 1-9. Benefiting from the decorated hydroxy moieties, HOF-FAFU-1 was exploited as a fluorescent sensor for hypochlorite detection in water media by a turn-off mode, which cannot be realized by its nonhydroxy groups anchoring counterpart (HOF-TCBP). The proposed sensing system is highly efficient, validated by a very broad linear range (0-0.45 mM), fast response (15 s), and small limit of detection (LOD) (1.32 μM). The fluorescent quenching of HOF-FAFU-1 toward hypochlorite was also investigated, mainly being ascribed to the transformation of building blocks from the fluorescent reduced state to the nonfluorescent oxidative state. This work not only demonstrates that HOFs integrated with high stability and large pores as well as high density of functional groups can be simultaneously realized by judicious design of building blocks but also conceptually elucidates that such HOFs can effectively extend the application fields of HOFs.
尽管氢键有机框架(HOFs)领域已取得巨大进展,但低稳定性、小孔径/无孔径以及功能化困难严重阻碍了它们的发展。在此,设计并在合成过程中轻松合成了一种新型的、具有高密度游离羟基部分修饰的坚固介孔HOF(HOF-FAFU-1)。在HOF-FAFU-1中,平面结构单元通过典型的分子间羧酸盐二聚体相互连接,形成具有拓扑结构的二维(2D)层,这些层通过面对面的π-π相互作用进一步与相邻层相连,从而获得三维(3D)开放介孔框架。由于分子间氢键的高密度和强π-π相互作用,HOF-FAFU-1非常稳定,使其能够在pH值为1-9的水溶液中保持其结构。受益于修饰的羟基部分,HOF-FAFU-1被用作水介质中次氯酸盐检测的荧光传感器,通过关闭模式实现,而其非羟基基团锚定的对应物(HOF-TCBP)则无法实现。所提出的传感系统效率很高,具有非常宽的线性范围(0-0.45 mM)、快速响应(15秒)和低检测限(LOD)(1.32 μM)。还研究了HOF-FAFU-1对次氯酸盐的荧光猝灭,主要归因于结构单元从荧光还原态转变为非荧光氧化态。这项工作不仅表明通过对结构单元的合理设计可以同时实现具有高稳定性、大孔径以及高密度官能团的HOFs,而且从概念上阐明了这种HOFs可以有效地扩展HOFs的应用领域。