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<p>Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation, yet it remains a long-standing challenge. As a common strategy, altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks (MOFs) and covalent organic frameworks (COFs), resulting in only a stepwise pore size variation of approximately 2.8 Å. Unlike MOFs and COFs, the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice. The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks, especially to achieve porous materials with the optimal pore size for D<sub>2</sub>/H<sub>2</sub> separation (∼3 Å). Here, we successfully modulate the porosity of supramolecular frameworks of [Co<sup>II</sup><sub>12</sub>Co<sup>III</sup><sub>8</sub>L<sub>12</sub>(<i>μ</i><sub>3</sub>-OH)<sub>24</sub>(X)]<sup>11+</sup> clusters (L = mono-deprotonated 1-iminoisoindole-3-amine, X = ClO<sub>4</sub><sup>−</sup> or Cl<sup>−</sup>) by controlling the duration of self-assembly processes. By simply adjusting the reaction time, we obtain three [Co<sup>II</sup><sub>12</sub>Co<sup>III</sup><sub>8</sub>L<sub>12</sub>(<i>μ</i><sub>3</sub>-OH)<sub>24</sub>(X)]<sup>11+</sup> supramolecular frameworks: [Co<sup>II</sup><sub>12</sub>Co<sup>III</sup><sub>8</sub>(<i>μ</i><sub>3</sub>-OH)<sub>24</sub>(ClO<sub>4</sub>)L<sub>12</sub>)]·(Cl)<sub>4</sub>·(HCO<sub>2</sub>)<sub>7</sub> (<b>1</b>), [Co<sup>II</sup><sub>12</sub>Co<sup>III</sup><sub>8</sub>L<sub>12</sub>(<i>μ</i><sub>3</sub>-OH)<sub>24</sub>(Cl)]·(ClO<sub>4</sub>)<sub>4</sub>·(Cl)<sub>6</sub>·(HCO<sub>2</sub>)·(H<sub>2</sub>O)<sub>10</sub> (<b>2</b>), and [Co<sup>II</sup>12Co<sup>III</sup><sub>8</sub>L<sub>12</sub>(<i>μ</i><sub>3</sub>-OH)<sub>24</sub>(Cl)]·(Cl)<sub>11</sub>·(H<sub>2</sub>O)<sub>12</sub> (<b>3</b>). The different stacking patterns of the [Co<sup>II</sup><sub>12</sub>Co<sup>III</sup><sub>8</sub>L<sub>12</sub>(<i>η</i><sub>3</sub>-OH)<sub>24</sub>(X)]<sup>11+</sup> clusters in these frameworks lead to significantly varied stabilities and porosities. Compound <b>1</b> exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions. In contrast, compound <b>2</b> is nearly nonporous, and compound <b>3</b> becomes unstable upon desolvation. The pores of compound <b>1</b> show higher affinity to D<sub>2</sub> than H<sub>2</sub>, and the pore aperture diameter of compound <b>1</b> (∼3.06 Å) meets the optimal porosity for D<sub>2</sub>/H<sub>2</sub> separation. Consequently, compound <b>1</b> demonstrates moderate D<sub>2</sub>/H<sub>2</sub> separation at 77 K (retention time: ∼7 min/g for D<sub>2</sub>/H<sub>2</sub>/Ne (10/10/80 vol%) in a flow of 5 mL/min). These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.</p>

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Tuning the porosity of {CoII12CoIII8(μ3-OH)24(X)}11+ supramolecular frameworks by reaction time for D2/H2 separation

  • 期刊论文

  • 发表日期：

    2025年1月7日

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  • Zhuozhou Xie,
  • Zhu Zhuo,
  • Zi-Ang Nan,
  • Qing Li,
  • Xiufang Li,
  • Zi-Xiu Lu,
  • Linzhe Lü,
  • Jin Liu,
  • Luyao Liu,
  • Wenjing Wang,
  • Wei Wang,
  • Daqiang Yuan,
  • You-Gui Huang

摘要

Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation, yet it remains a long-standing challenge. As a common strategy, altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks (MOFs) and covalent organic frameworks (COFs), resulting in only a stepwise pore size variation of approximately 2.8 Å. Unlike MOFs and COFs, the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice. The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks, especially to achieve porous materials with the optimal pore size for D2/H2 separation (∼3 Å). Here, we successfully modulate the porosity of supramolecular frameworks of [CoII12CoIII8L12(μ3-OH)24(X)]11+ clusters (L = mono-deprotonated 1-iminoisoindole-3-amine, X = ClO4− or Cl−) by controlling the duration of self-assembly processes. By simply adjusting the reaction time, we obtain three [CoII12CoIII8L12(μ3-OH)24(X)]11+ supramolecular frameworks: [CoII12CoIII8(μ3-OH)24(ClO4)L12)]·(Cl)4·(HCO2)7 (1), [CoII12CoIII8L12(μ3-OH)24(Cl)]·(ClO4)4·(Cl)6·(HCO2)·(H2O)10 (2), and [CoII12CoIII8L12(μ3-OH)24(Cl)]·(Cl)11·(H2O)12 (3). The different stacking patterns of the [CoII12CoIII8L12(η3-OH)24(X)]11+ clusters in these frameworks lead to significantly varied stabilities and porosities. Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions. In contrast, compound 2 is nearly nonporous, and compound 3 becomes unstable upon desolvation. The pores of compound 1 show higher affinity to D2 than H2, and the pore aperture diameter of compound 1 (∼3.06 Å) meets the optimal porosity for D2/H2 separation. Consequently, compound 1 demonstrates moderate D2/H2 separation at 77 K (retention time: ∼7 min/g for D2/H2/Ne (10/10/80 vol%) in a flow of 5 mL/min). These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.