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<p>In general, flexible metal-organic frameworks (MOFs) change their structures via framework breathing in response to external stimuli (usually guest adsorption and desorption). Here, we show a dynamic coordination bond in a flexible MOF driving a thermo-induced diffuse phase transition occurring in a wide temperature range of 130–270 K (centered at ∼200 K), which enables the switching of magnetism and second-harmonic generation (SHG) responses. In specific, a solvent-free Co<sup>II</sup>-based flexible MOF Co<sub>2</sub>(TPY)<sub>2</sub>(BPTC) (<b>1</b>), bearing biphenyl-3,3′,5,5′-tetracarboxylic acid (H<sub>4</sub>BPTC) and 2,2′:6′,2″-terpyridine (TPY) ligands, exhibits a reversible thermo-responsive coordination-mode switching between five- and six-fold. This dynamic bond results in the reversible transformation between a distorted polar framework and a regular nonpolar framework, and therefore leads to the subtle change of the magnetic property and substantial change of the nonlinear optical property of <b>1</b>.</p>

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A thermally reversible dynamic bond as a magnetic and nonlinear optical switch

  • 期刊论文

  • 发表日期：

    2025年3月17日

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  • Xue-Li Cao,
  • Jin Liu,
  • Chuan-Qi Shen,
  • Shu-Qi Wu,
  • Zi-Shuo Yao,
  • Qing Li,
  • Zhong-Min Cao,
  • Lu-Yao Liu,
  • Fu-Lin Lin,
  • Zi-Ang Nan,
  • Zhu Zhuo,
  • Wei Wang,
  • Osamu Sato,
  • You-Gui Huang

摘要

In general, flexible metal-organic frameworks (MOFs) change their structures via framework breathing in response to external stimuli (usually guest adsorption and desorption). Here, we show a dynamic coordination bond in a flexible MOF driving a thermo-induced diffuse phase transition occurring in a wide temperature range of 130–270 K (centered at ∼200 K), which enables the switching of magnetism and second-harmonic generation (SHG) responses. In specific, a solvent-free CoII-based flexible MOF Co2(TPY)2(BPTC) (1), bearing biphenyl-3,3′,5,5′-tetracarboxylic acid (H4BPTC) and 2,2′:6′,2″-terpyridine (TPY) ligands, exhibits a reversible thermo-responsive coordination-mode switching between five- and six-fold. This dynamic bond results in the reversible transformation between a distorted polar framework and a regular nonpolar framework, and therefore leads to the subtle change of the magnetic property and substantial change of the nonlinear optical property of 1.