Spirobifluorene-Based Three-Dimensional Covalent Organic Frameworks with Rigid Topological Channels as Efficient Heterogeneous Catalyst  

作　　者：Yamei Liu Chenyu Wu Qingzhu Sun Fan Hu Qingyan Pan Jing Sun Yinghua Jin Zhibo Li Wei Zhang Yingjie Zhao 

机构地区：[1]College of Polymer Science and Engineering,Qingdao University of Science and Technology,Qingdao 266042 [2]Department of Chemistry,University of Colorado,Boulder,CO 80309 [3]School of Chemical Engineering,The University of New South Wales,Sydney,NSW 2052

出　　处：《CCS Chemistry》2021年第4期2418-2427,共10页中国化学会会刊（英文）

基　　金：The work was supported by the National Natural Science Foundation of China(nos.51722302,21674054,and 51972185).

摘　　要：Although the past decade has witnessed tremendous progress in the development of covalent organic frameworks(COFs),three-dimensional(3D)COFs fabrications and characterizations are still much less studied compared with two-dimensional(2D)COFs,due to their complicated topology structures caused by interpenetration and limited choices of node-building blocks.In this work,we constructed a novel 3D COF(SP-3D-COF-BPY)successfully using orthogonal dual-planar spirobifluorene and bipyridine as building blocks.Also,we demonstrated the application of 3D COF-supported Pd(II)catalyst in heterogeneous catalysis.A sevenfold interpenetrated dia structure was revealed for SP-3DCOF-BPY by powder X-ray diffraction(PXRD)in conjunction with structural simulation and Pawley refinement.The bipyridine-linked frameworks bear one-dimensional(1D)unobstructed rigid channels and offer a high density of discrete coordination sites for chelating Pd(II)species.Very high loading of Pd(II)(∼15 wt%)was achieved in the asymmetric(as)-prepared Pd(II)@3D-COF-BYP.The generated highly ordered porous channels and easily accessible catalytic sites,such as COF-supported Pd(II)complex,serves as a highly active and stable microporous heterogeneous catalyst in Suzuki–Miyaura coupling reactions.The observed catalytic efficiency was high and the catalyst could be conveniently reused multiple times without any noticeable decay in catalytic performance.

关 键 词：covalent organic frameworks SPIROBIFLUORENE heterogeneous catalysis PALLADIUM Suzuki-Miyaura coupling 

分 类 号：O64[理学—物理化学]