Kurz Hannah, Teeuwen Paula C P, Ronson Tanya K, Hoffman Jack B, Pracht Philipp, Wales David J, Nitschke Jonathan R
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
J Am Chem Soc. 2024 Nov 13;146(45):30958-30965. doi: 10.1021/jacs.4c09742. Epub 2024 Nov 4.
A key feature of coordination cages is the dynamic nature of their coordinative bonds, which facilitates the synthesis of complex polyhedral structures and their post-assembly modification. However, this dynamic nature can limit cage stability. Increasing cage robustness is important for real-world use cases. Here we introduce a double-bridging strategy to increase cage stability, where designed pairs of bifunctional subcomponents combine to generate rectangular tetratopic ligands within pseudo-cubic ZnL cages. These cages withstand transmetalation, the addition of competing ligands, and nucleophilic imines, under conditions where their single-bridged congeners decompose. Our approach not only increases the stability and robustness of the cages while maintaining their polyhedral structure, but also enables the incorporation of additional functional units in proximity to the cavity. The double-bridging strategy also facilitates the synthesis of larger cages, which are inaccessible as single-bridged congeners.
配位笼的一个关键特性是其配位键的动态性质，这有利于复杂多面体结构的合成及其组装后修饰。然而，这种动态性质可能会限制笼的稳定性。提高笼的稳健性对于实际应用案例很重要。在此，我们引入一种双桥连策略来提高笼的稳定性，即设计的双功能子组件对组合形成伪立方ZnL笼内的矩形四齿配体。在其单桥连同类物分解的条件下，这些笼能经受住金属转移、竞争性配体的添加以及亲核亚胺。我们的方法不仅在保持笼的多面体结构的同时提高了其稳定性和稳健性，还能在靠近空腔处引入额外的功能单元。双桥连策略还促进了更大笼的合成，而单桥连同类物无法合成出更大的笼。
