Three‐Dimensional Crystalline Covalent Triazine Frameworks via a Polycondensation Approach

Abstract The growth of crystalline covalent triazine frameworks (CTFs) is still considered as a great challenge due to the less reversible covalent bonds of triazine linkages. The research studies of crystalline CTFs to date have been limited to two‐dimensional (2D) structures, and the three‐dimensional (3D) crystalline CTFs have never been reported before. Herein we report the design and synthesis of two 3D crystalline CTFs, termed 3D CTF‐TPM and 3D CTF‐TPA through a reversible/irreversible polycondensation approach. The targeted 3D CTFs adopt ctn topology, and show moderate crystallinity, relatively large surface area (ca. 2000 m 2 g −1 ), and high CO 2 uptake capacity (23.61 wt.%). Moreover, these 3D CTFs exhibit ultrastability in the presence of boiling water, strong acid (1 M HCl) and strong base (1 M NaOH). This contribution represents the first report of 3D crystalline CTFs, which not only extends their structural diversity but also offers a synthetic strategy and structural basis for expanding practical applications of CTF materials.