Inorganic macrocycles remain largely underdeveloped compared with their organic counterparts due to the challenges involved in their synthesis. Among them, cyclodiphosphazane macrocycles have shown to be promising candidates for supramolecular chemistry applications due to their ability to encapsulate small molecules or ions within their cavities. However, further developments have been handicapped by the lack of synthetic routes to high-order cyclodiphosphazane macrocycles. Moreover, current approaches allow little control over the size of the macrocycles formed. Here we report the synthesis of high-order oxygen-bridged phosphazane macrocycles via a “3 + n cyclisation” (n = 1 and 3). Using this method, an all-P^III high-order hexameric cyclodiphosphazane macrocycle was isolated, displaying a larger macrocyclic cavity than comparable organic crown-ethers. Our approach demonstrates that increasing building block complexity enables precise control over macrocycle size, which will not only generate future developments in both the phosphazane and main group chemistry but also in the fields of supramolecular chemistry.

由于合成过程中的挑战，无机大环化合物与有机大环化合物相比在很大程度上仍未得到充分开发。其中，环二磷氮烷大环化合物已被证明是超分子化学应用的有前途的候选者，因为它们能够将小分子或离子封装在其空腔内。然而，由于缺乏高阶环二磷氮烷大环化合物的合成路线，进一步的发展受到了阻碍。此外，目前的方法几乎无法控制所形成的大环的大小。在这里，我们报告了通过“ 3  +  n环化”（n  = 1 和 3）合成高阶氧桥磷氮烷大环化合物。使用这种方法，一个全 P ^III分离出高阶六聚环二磷氮烷大环，显示出比同类有机冠醚更大的大环空腔。我们的方法表明，增加结构单元的复杂性可以精确控制大环的大小，这不仅会在磷氮烷和主基团化学以及超分子化学领域产生未来的发展。