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<p>Developing and understanding the topochemical polymerization behavior of metal-organic frameworks (MOFs) exhibits great potential for synthesizing crystalline polymers for various applications, however, it is still a challenging task under pressure treatment. Herein, we study the pressure-induced topochemical polymerization of MOFs on their photoluminescence property. The pillar-layered diacetylene MOFs possess favorable stacking orientation and spatial arrangement between the diacetylene ligands. Such orientation and compact arrangements prompt the topochemical polymerization via 1,4-addition reactions, driven by the lattice compression upon pressure. The lattice compression and topochemical polymerization have been demonstrated by <i>in situ</i> high-pressure XRD patterns and Raman spectra. Additionally, three diacetylene MOFs exhibited distinct piezo-fluorochromic properties, including emission changes and wavelength shifts with increasing pressure. This study not only demonstrates the potential of designing pressure-responsive MOFs based on topochemical polymerization but also provides direct support for elucidating the ambiguous mechanism of pressure response and a new strategy for regulating optical properties.</p>

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Pressure-inducing topochemical polymerization on metal-organic frameworks

  • 期刊论文

  • 发表日期：

    2025年5月28日

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  • Zhi-Bin Jin,
  • Yongfu Liang,
  • Wenming Tian,
  • Zhi-Gang Gu,
  • Jian Zhang

摘要

Developing and understanding the topochemical polymerization behavior of metal-organic frameworks (MOFs) exhibits great potential for synthesizing crystalline polymers for various applications, however, it is still a challenging task under pressure treatment. Herein, we study the pressure-induced topochemical polymerization of MOFs on their photoluminescence property. The pillar-layered diacetylene MOFs possess favorable stacking orientation and spatial arrangement between the diacetylene ligands. Such orientation and compact arrangements prompt the topochemical polymerization via 1,4-addition reactions, driven by the lattice compression upon pressure. The lattice compression and topochemical polymerization have been demonstrated by in situ high-pressure XRD patterns and Raman spectra. Additionally, three diacetylene MOFs exhibited distinct piezo-fluorochromic properties, including emission changes and wavelength shifts with increasing pressure. This study not only demonstrates the potential of designing pressure-responsive MOFs based on topochemical polymerization but also provides direct support for elucidating the ambiguous mechanism of pressure response and a new strategy for regulating optical properties.