Calixarene compounds are widely used in molecular recognition, complexation, extraction, catalysis, medicine, etc., and these properties are closely related to the bonded metal ions. Although the metal clusters constructed using calixarene and its derivatives have achieved great progress, Al clusters based on these macrocyclic ligands are still in the preliminary research stage due to the obvious hydrolysis of Al³⁺ ions in solution. It is a great challenge to obtain high-quality measurable single crystals of aluminum oxo clusters (AlOCs). Herein, we used an oxygen-rich organic macrocyclic ligand of p-tertbutylsulfonylcalix[4]arene (H₄BTC4A-SO₂) to synthesize three Al₄ clusters with formulas Al₄(OH)₂(BTC4A-SO₂)₂(MeO)₂(DMA)₂(MeOH)₂ (Al₄-DMA·MeOH), Al₄(OH)₄(BTC₄A-SO₂)₂(DMA)₄ (Al₄-DMA), and Al₄(OH)₄(BTC4A-SO₂)₂(DMF)₄ (Al₄-DMF) which are combined by different solvents. Interestingly, the cycloaddition of carbon dioxide proves that the three AlOCs with different coordinated solvents exhibit different catalytic activities and Al₄-DMF shows the highest catalytic yield up to 99%. This work not only reveals three interesting calixarene-based Al cluster structures, but also realizes the regulation of catalytic activities for the reaction of the cycloaddition of carbon dioxide. This provides insights into the assembly of AlOCs and their study as catalysts.

中文翻译：

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磺酰卡利克斯[4]芳烃基 Al4 簇：三个铝簸簇，具有不同的配位溶剂，用于 CO2 环加成反应


卡利沙芳烃化合物广泛用于分子识别、络合、萃取、催化、医药等，这些性质与键合金属离子密切相关。尽管使用卡利沙芳烃及其衍生物构建的金属团簇取得了长足的进展，但由于 Al³⁺ 离子在溶液中明显水解，基于这些大环配体的 Al 团簇仍处于初步研究阶段。获得高质量的可测量铝簸簇 （AlOCs） 单晶是一项巨大的挑战。在本文中，我们使用对叔丁基磺酰卡利克斯[4]芳烃 （H₄BTC4A-SO₂） 的富氧有机大环配体合成了三个 Al₄ 簇，分子式为 Al₄（OH）₂（BTC4A-SO₂）₂（MeO）₂（DMA）₂（MeOH）₂ （Al₄-DMA·甲醇）、铝₄（OH）₄（BTC₄A-SO₂）₂（DMA）₄ （铝_4-DMA） 和铝₄（OH）₄（BTC4A-SO₂）₂（DMF）₄ （铝_4-DMF）），它们由不同的溶剂混合而成。 有趣的是，二氧化碳的环加成反应证明，具有不同配位溶剂的三种 AlOCs 表现出不同的催化活性，而 Al_4-DMF 显示出最高的催化产率，高达 99%。这项工作不仅揭示了三种有趣的基于卡利沙芳烃的 Al 团簇结构，还实现了对二氧化碳环加成反应催化活性的调节。这为 AlOCs 的组装及其作为催化剂的研究提供了见解。