We have synthesized a completely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, NⁱPr, N^tBu and NPh bridging groups. In addition, the first NH‐bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from ≈6 to ≈10 Å). Moreover, these species exhibit pronounced topological changes when a weak non‐bonding NH⋅⋅⋅π aryl interaction is introduced. Finally, the NH‐bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host–guest applications.

中文翻译：

---

N桥无环三聚聚环二磷氮烷：高度可调的环二磷氮烷构件。

我们已经合成了一个全新的无环三聚环二磷氮烷化合物家族，该化合物包括NH，N ⁱ Pr，N ^tBu和NPh桥接组。此外，还生产了第一个NH桥无环二聚环磷氮烷。三聚体物种显示出高度可调节的特性，因此末端N（H）R部分之间的距离可以很容易地通过桥基中存在的空间体积（从≈6到≈10Å）进行调节。此外，当引入弱的非键性NH⋅⋅⋅π芳基相互作用时，这些物质表现出明显的拓扑变化。最后，已经计算了NH桥联的氯离子结合亲和力，以及可用于单体环二磷氮烷的现有实验数据作为基准。我们的结果强调了这些物种是超分子宿主-客体应用中有希望的氢键供体。