Synthesis of Single-Crystal Two-Dimensional Covalent Organic Frameworks and Uncovering Their Hidden Structural Features by Three-Dimensional Electron Diffraction.

Two-dimensional covalent organic frameworks (2D COFs) are formed by the polycondensation of geometrically specific monomers to grow covalently connected 2D polygonal polymers over the - plane and supramolecular polymerization and/or crystallization of 2D sheets along the direction to constitute layer architectures. Despite various efforts, the synthesis of single-crystal 2D COFs remains a challenging goal. Here, we report the synthesis of single-crystal 2D COFs, by taking the representative imine-linked TPB-DMTP-COF as an example, to reveal the key synthetic parameters that control the crystallization of 2D COFs.

Wiring Covalent Organic Frameworks with Conducting Polymers.

Covalent organic frameworks are a class of crystalline porous polymers formed by linking organic units into periodically aligned skeletons and pores. Here we report a strategy for wiring these frameworks with conducting polymers via wall engineering and polymerization. We anchored each edge site with one pyrrole unit, which is densely packed along the z direction yet protruded from pore walls.