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3D Porphyrin-Based Covalent Organic Frameworks
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-06-15 00:00:00 , DOI: 10.1021/jacs.7b04141
Guiqing Lin 1 , Huimin Ding 1 , Rufan Chen 1 , Zhengkang Peng 1 , Baoshan Wang 1 , Cheng Wang 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-06-15 00:00:00 , DOI: 10.1021/jacs.7b04141
Guiqing Lin 1 , Huimin Ding 1 , Rufan Chen 1 , Zhengkang Peng 1 , Baoshan Wang 1 , Cheng Wang 1
Affiliation
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The design and synthesis of three-dimensional covalent organic frameworks (3D COFs) bearing photoelectric units have been considered as a big challenge. Herein, for the first time, we reported the targeted synthesis of two 3D porphyrin-based COFs (3D-Por-COF and 3D-CuPor-COF), starting from tetrahedral (3D-Td) and square (2D-C4) building blocks connected through [4 + 4] imine condensation reactions. On the basis of structural characterizations, 3D-Por-COF and 3D-CuPor-COF are microporous materials with high surface areas, and are proposed to adopt a 2-fold interpenetrated pts topology with Pmc21 space group. Interestingly, both 3D COFs are photosensitive and can be used as heterogeneous catalyst for generating singlet oxygen under photoirradiation. However, 3D-Por-COF shows enhanced photocatalytic activity compared with 3D-CuPor-COF, indicating the properties of 3D porphyrin-based COFs can be tuned by metalation of porphyrin rings. The results reported here will greatly inspire us to design and synthesize 3D COFs bearing other metalloporphyrins for interesting applications (e.g., catalysis) in the future.
中文翻译：
基于3D卟啉的共价有机框架
带有光电单元的三维共价有机骨架（3D COF）的设计和合成已被认为是一个巨大的挑战。在此，我们首次报道了从四面体（3D- T d）和正方形（2D- C 4）开始的两种基于3D卟啉的COF（3D-Por-COF和3D-CuPor-COF）的靶向合成。通过[4 + 4]亚胺缩合反应连接的结构单元。根据结构特征，3D-Por-COF和3D-CuPor-COF是具有高表面积的微孔材料，建议采用2倍互穿的pts拓扑结构，且Pmc 2 1空间群。有趣的是，两种3D COF都是光敏的，可以用作在光辐照下产生单线态氧的非均相催化剂。但是，与3D-CuPor-COF相比，3D-Por-COF显示出增强的光催化活性，这表明可以通过卟啉环的金属化来调节基于3D卟啉的COF的特性。此处报道的结果将极大地启发我们设计和合成带有其他金属卟啉的3D COF，以便将来用于有趣的应用（例如催化）。
更新日期：2017-06-28
中文翻译：
基于3D卟啉的共价有机框架
带有光电单元的三维共价有机骨架（3D COF）的设计和合成已被认为是一个巨大的挑战。在此，我们首次报道了从四面体（3D- T d）和正方形（2D- C 4）开始的两种基于3D卟啉的COF（3D-Por-COF和3D-CuPor-COF）的靶向合成。通过[4 + 4]亚胺缩合反应连接的结构单元。根据结构特征，3D-Por-COF和3D-CuPor-COF是具有高表面积的微孔材料，建议采用2倍互穿的pts拓扑结构，且Pmc 2 1空间群。有趣的是，两种3D COF都是光敏的，可以用作在光辐照下产生单线态氧的非均相催化剂。但是，与3D-CuPor-COF相比，3D-Por-COF显示出增强的光催化活性，这表明可以通过卟啉环的金属化来调节基于3D卟啉的COF的特性。此处报道的结果将极大地启发我们设计和合成带有其他金属卟啉的3D COF，以便将来用于有趣的应用（例如催化）。
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