Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 8, Pages 3718-3723Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b13824
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Funding
- National Natural Science Foundation of China [21871009, 21621061, 21527803, 21772149, 21572170]
- Funds for Creative Research Groups of Hubei Province [2017CFA002]
- Fundamental Research Funds for Central Universities
- Swedish Research Council (VR)
- Knut and Alice Wallenberg Foundation (KAW)
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Rational construction of covalent organic frameworks (COFs) with novel structures still remains a challenge. Herein, we report the designed synthesis of two COFs, 2D-BPTA-COF and 3D-BMTA-COF, starting from biphenyl-based precursors but with different groups at the 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 7-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 similar to 0 degrees while in 3D-BMTA-COF it is similar to 60 degrees. 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 diversity of tetrahedral nodes for constructing 3D COFs in the future, and moreover, a new tetrahedral node for constructing 3D COFs is now available.
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