Topology‐Templated Synthesis of Crystalline Porous Covalent Organic Frameworks

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 2 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 2 carbon frameworks with tetragonal, hexagonal, and kagome topologies. The sp 2 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 2 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.