Crystallization of Dimensional Isomers in Covalent Organic Frameworks.

Dimensional isomers, defined in reticular chemistry as frameworks consisting of identical molecular building blocks but extended in two or three dimensions (2D or 3D), are an important type of framework isomers that have never been isolated. Herein, we report the crystallization of dimensional isomers in covalent organic frameworks (COFs) for the first time. By polymerization of the same molecular building blocks at different temperatures, both 2D and 3D COFs were successfully constructed due to the temperature-induced conformational changes of precursors from planar to tetrahedral. In addition, the non-fluorescent 2D COF can be gradually converted into the fluorescent 3D COF by increasing the temperature under solvothermal conditions. Therefore, it is reasonable to crystallize the dimensional isomers of reticular materials by controlling the conformation of molecular building blocks, and more examples can be expected. Since the obtained dimensional isomers show different properties and functions, this work will definitely motivate us to design reticular materials for target applications in the future.