4.8 Article

Polymorphism of 2D Imine Covalent Organic Frameworks

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 10, Pages 5363-5369

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202015130

Keywords

controllable growth; covalent organic frameworks; isomers; selective adsorption

Funding

  1. National Key Research and Development Program of China [2017YFA0207500]
  2. National Natural Science Foundation of China [51973153, 21975049, 21875140]
  3. Natural Science Foundation of Tianjin [17JCJQJC44600]

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The study designed and synthesized different isomeric tetraphenyl benzene monomers to construct various frameworks by changing reaction solvents. The geometry of monomers was found to influence lattice growth process, with the frameworks exhibiting highly selective adsorption of vitamin B-12.
We designed and synthesized A(2)B(2) type tetraphenyl benzene monomers (p-, m-, and o-TetPB) which have the para-, meta, and ortho-substituted isomeric structures, for the direct construction of isomeric frameworks. Interestingly, both kagome (kgm) and monoclinic square (sql) framework isomers are produced from either p-TetPB (C-2h symmetry) or m-TetPB (C-2v symmetry) by changing reaction solvents, while their isomeric structures are characterized by X-ray diffraction, computational simulation, microscopy, and sorption isotherm measurements. Only sql frameworks was formed for o-TetPB (C-2v symmetry), irrespective of reaction solvents. These results disclose a unique feature in the framework structural formation, that is, the geometry of monomers directs and dominates the lattice growth process while the solvent plays a role in the perturbation of chain growth pattern. The isomeric frameworks exhibit highly selective adsorption of vitamin B-12 owing to pore shape and size differences.

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