Highly porous metal–organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of ‘sacrificial’ bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF’s copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

在过去的几十年中，高度多孔的金属有机框架（MOF）经历了令人激动的发展，显示出了广泛的应用前景。但是，许多研究表明，它们遭受了重大的稳定性问题，尤其是在与水的相互作用方面，这严重限制了它们的实际应用潜力。在这里，我们证明了在其金属中心的配位环境中“牺牲”键的存在（称为半合性）如何赋予了脱水铜基MOF良好的水解稳定性。暴露于水后，与通常会导致结构退化的配偶键的不加区别地形成对比的是，MOF的铜桨轮簇之间的非结构性弱相互作用被破坏，框架恢复了其合成后的状态，水合的结构。即使在与水接触一年后，该MOF仍保持其结构完整性，而在相同条件下不到一天的时间内，缺乏这些牺牲性键的组成相似的材料HKUST-1便失去了结晶性。