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<p>Covalent organic frameworks (COFs) are crystalline porous polymers traditionally assembled via reversible condensation polymerizations to form ordered structures. In contrast, coupling reactions have historically led to amorphous, disordered materials due to their irreversible nature, posing a challenge for COF synthesis. Here we present a microinterfacial solvothermal polymerization strategy that overcomes this limitation by harnessing irreversible coupling reactions to construct crystalline porous framework materials. By spatially confining monomers and intermediates at organic–water interfaces, our approach drives Glaser–Eglinton coupling polymerization of ethynyl-functionalized monomers to form two-dimensional <i>sp</i>-carbon-conjugated COFs with discrete hexagonal, tetragonal and kagome topologies. The resulting frameworks allow extended in-plane <i>π</i> conjugation and out-of-plane electronic coupling and exhibit an eight-order-of-magnitude enhancement in electrical conductivity upon chemical oxidation with iodine in pores. These materials confine free radicals at nodal sites, where their spins are aligned in different ways to develop paramagnetic, antiferromagnetic and ferromagnetic phases, evolving semiconducting magnets with distinct spin coherence controlled by the COF topology. These findings showcase the use of coupling reactions in COF synthesis to synthesize an interesting class of organic semiconducting magnets.</p><p></p>

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Synthesis of covalent organic frameworks via coupling polymerization

  • 期刊论文

  • 发表日期：

    2025年9月24日

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  • Zhuoer Li,
  • Shanshan Tao,
  • Matthew Addicoat,
  • Toshikazu Nakamura,
  • Donglin Jiang

摘要

Covalent organic frameworks (COFs) are crystalline porous polymers traditionally assembled via reversible condensation polymerizations to form ordered structures. In contrast, coupling reactions have historically led to amorphous, disordered materials due to their irreversible nature, posing a challenge for COF synthesis. Here we present a microinterfacial solvothermal polymerization strategy that overcomes this limitation by harnessing irreversible coupling reactions to construct crystalline porous framework materials. By spatially confining monomers and intermediates at organic–water interfaces, our approach drives Glaser–Eglinton coupling polymerization of ethynyl-functionalized monomers to form two-dimensional sp-carbon-conjugated COFs with discrete hexagonal, tetragonal and kagome topologies. The resulting frameworks allow extended in-plane π conjugation and out-of-plane electronic coupling and exhibit an eight-order-of-magnitude enhancement in electrical conductivity upon chemical oxidation with iodine in pores. These materials confine free radicals at nodal sites, where their spins are aligned in different ways to develop paramagnetic, antiferromagnetic and ferromagnetic phases, evolving semiconducting magnets with distinct spin coherence controlled by the COF topology. These findings showcase the use of coupling reactions in COF synthesis to synthesize an interesting class of organic semiconducting magnets.