Twist Building Blocks from Planar to Tetrahedral for the Synthesis of Covalent Organic Frameworks.

Rational construction of covalent organic frameworks (COFs) with novel structures still remains a challenge. Herein, we report-ed the designed synthesis of two COFs, 2D-BPTA-COF and 3D-BMTA-COF, starting from biphenyl-based precursors but with different groups on ortho positions. Both COFs exhibited high crystallinity and large surface area, and interestingly, 2D-BPTA-COF crystallizes into 2D sheets with AB stacking mode while 3D-BMTA-COF adopts a seven-fold interpenetrated structure with pts topology. This structural difference could be ascribed to the introduction of methyl groups in the building blocks, as the dihedral angle of biphenyl rings in 2D-BPTA-COF is ~0° while in 3D-BMTA-COF is ~60°. Therefore, it is possible to synthesize COFs with different structures by twisting building blocks from planar to tetrahedral with steric hindrance. We believe this result represents a general and straightforward way to expand the diver-sity of tetrahedral nodes for constructing 3D COFs in future, and moreover, a new tetrahedral node for constructing 3D COFs is now available.