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Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall

Lars Grunenberg1,2, Gökcen Savasci1,2,3, Maxwell W Terban1

  • 1Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany.

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|February 24, 2021
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Summary

Researchers developed a new method to create amine-linked covalent organic frameworks (COFs). These advanced materials offer tunable properties and enhanced stability for applications in catalysis.

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Area of Science:

  • Materials Science
  • Organic Chemistry
  • Polymer Chemistry

Background:

  • Covalent organic frameworks (COFs) are crystalline polymers with tunable properties.
  • Existing COF synthesis methods have limitations in functionalization and stability.

Purpose of the Study:

  • To develop a novel strategy for directly synthesizing amine-linked COFs.
  • To enable pore-wall modification and linkage interconversion in COFs.
  • To create COFs with enhanced hydrolytic stability for catalytic applications.

Main Methods:

  • Utilized Leuckart-Wallach reduction with formic acid and ammonium formate.
  • Employed a one-pot crystallization-reduction approach.
  • Synthesized amine-linked COFs (rPI-3-COF, rTTI-COF, rPy1P-COF) from imine-linked precursors or linkers.

Main Results:

  • Achieved direct synthesis of amine-linked COFs with high crystallinity and large surface areas.
  • Generated frameworks with secondary amine linkages, mixed amine/imine bonds, and formylated amine linkages.
  • Demonstrated postsynthetic functionalization of pore walls via secondary amines.

Conclusions:

  • The new method provides access to versatile amine-linked COFs.
  • These COFs exhibit improved hydrolytic stability and potential as heterogeneous catalysts.
  • The strategy allows for tailored functionalization for specific applications.