文献类型：期刊文献

英文题名：2D to 3D Reconstruction of Boron-Linked Covalent-Organic Frameworks

作者：Wang, Xue[1,2];Fellowes, Thomas[1,2];Bahri, Mounib[3];Qu, Hang[2];Li, Boyu[2];Niu, Hongjun[2];Browning, Nigel D.[3];Zhang, Weiwei[4];Ward, John W.[1,2];Cooper, Andrew I.[1,2]

机构：[1]Univ Liverpool, Leverhulme Res Ctr Funct Mat Design, Liverpool L7 3NY, England;[2]Univ Liverpool, Dept Chem & Mat Innovat Factory, Liverpool L69 7ZD, England;[3]Univ Liverpool, Albert Crewe Ctr Electron Microscopy, Liverpool L69 3GL, England;[4]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：146

期号：20

起止页码：14128

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20242016089141);WOS:【SCI-EXPANDED(收录号:WOS:001224816400001)】；

基金：For funding, the authors acknowledge the Leverhulme Trust via the Leverhulme Research Centre for Functional Materials Design and the Engineering and Physical Sciences Research Council (EPSRC) (EP/N004884/1). W.Z. acknowledges the National Natural Science Foundation of China (22375062), Shanghai Pilot Program for Basic Research (22TQ1400100-10), Shanghai Pujiang Program (22PJ1402400), the "Chenguang Program" supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (22CGA32), and the Young Elite Scientists Sponsorship Program by CAST (2023QNRC001). We thank Dr. Xiaoyan Wang for useful discussions on the draft preparation. X.W. thanks Dr. Linjiang Chen for all the inspirational discussions and generous support during this project.

语种：英文

外文关键词：Cobalt compounds - Esters - Hydrocarbons - Image reconstruction - Pore size

摘要：The transformation of two-dimensional (2D) covalent-organic frameworks (COFs) into three-dimensions (3D) is synthetically challenging, and it is typically addressed through interlayer cross-linking of alkene or alkyne bonds. Here, we report the first example of the chemical reconstruction of a 2D COF to a 3D COF with a complete lattice rearrangement facilitated by base-triggered boron hybridization. This chemical reconstruction involves the conversion of trigonal boronate ester linkages to tetrahedral anionic spiroborate linkages. This transformation reticulates the coplanar, closely stacked square cobalt(II) phthalocyanine (PcCo) units into a 3D perpendicular arrangement. As a result, the pore size of COFs expands from 2.45 nm for the initial 2D square lattice (sql) to 3.02 nm in the 3D noninterpenetrated network (nbo). Mechanistic studies reveal a base-catalyzed boronate ester protodeboronation pathway for the formation of the spiroborate structure.