Three‐Dimensional Crystalline Covalent Triazine Frameworks via a Polycondensation Approach

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 m2 g-1 ), and high CO2 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.