Jin Enquan, Geng Keyu, Lee Ka Hung, Jiang Weiming, Li Juan, Jiang Qiuhong, Irle Stephan, Jiang Donglin
Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore.
Computational Sciences and Engineering Division & Chemical Sciences Division, Oak Ridge National Laboratory, USA.
Angew Chem Int Ed Engl. 2020 Jul 13;59(29):12162-12169. doi: 10.1002/anie.202004728. Epub 2020 May 18.
A strategy is presented for the synthesis of crystalline porous covalent organic frameworks via topology-templated polymerization. The template is based on imine-linked frameworks and their (001) facets seed the C=C bond formation reaction to constitute 2D sp carbon-conjugated frameworks. This strategy is applicable to templates with different topologies, enables designed synthesis of frameworks that cannot be prepared via direct polymerization, and creates a series of sp carbon frameworks with tetragonal, hexagonal, and kagome topologies. The sp carbon frameworks are highly luminescent even in the solid state and exhibit topology-dependent π transmission and exciton migration; these key fundamental π functions are unique to sp carbon-conjugated frameworks and cannot be accessible by imine-linked frameworks, amorphous analogues, and 1D conjugated polymers. These results demonstrate an unprecedented strategy for structural and functional designs of covalent organic frameworks.
本文提出了一种通过拓扑模板聚合合成结晶多孔共价有机框架的策略。该模板基于亚胺连接的框架，其(001)面引发C=C键形成反应，以构成二维sp碳共轭框架。该策略适用于具有不同拓扑结构的模板，能够设计合成无法通过直接聚合制备的框架，并创建了一系列具有四方、六角和 kagome 拓扑结构的sp碳框架。这些sp碳框架即使在固态下也具有高发光性，并表现出拓扑依赖性的π传输和激子迁移；这些关键的基本π功能是sp碳共轭框架所特有的，亚胺连接的框架、无定形类似物和一维共轭聚合物无法实现。这些结果展示了一种前所未有的共价有机框架结构和功能设计策略。
