We have prepared a photoresponsive metal-organic framework by using an amide-based [2]rotaxane as linker and copper(II) ions as metal nodes. The interlocked linker was obtained by the hydrogen bond-directed approach employing a fumaramide thread as template of the macrocyclic component, this latter incorporating two carboxyl groups. Single crystal X-ray diffraction analysis of the metal-organic framework, prepared under solvothermal conditions, showed the formation of stacked 2D rhombohedral grids forming channels decorated with the interlocked alkenyl threads. A series of metal-organic frameworks differing in the E/Z olefin ratio were prepared either by the previous isomerization of the linker or by post-irradiation of the reticulated materials. By dynamic solid state 2H NMR measurements, using deuterium-labelled materials, we proved that the geometry of the olefinic axis of the interlocked struts determined the obtention of materials with different independent local dynamics as a result of the strength of the intercomponent non-covalent interactions. Moreover, the usefulness of these novel copper-rotaxane materials as molecular dosing containers has also been assayed by the diffusion and photorelease of p-benzoquinone, evaluated in different solvents and temperatures.

中文翻译：

---

用于构建具有受控货物交付的光响应金属有机框架的铜连接轮烷

我们通过使用基于酰胺的 [2] 轮烷作为接头和铜 (II) 离子作为金属节点制备了光响应金属有机框架。互锁接头是通过氢键定向方法获得的，采用富马酰胺线作为大环组分的模板，后者结合了两个羧基。在溶剂热条件下制备的金属-有机骨架的单晶 X 射线衍射分析表明，堆叠的 2D 菱面体网格的形成形成了用互锁链烯基线装饰的通道。一系列 E/Z 烯烃比不同的金属-有机骨架通过连接体的先前异构化或通过网状材料的后辐照制备。通过动态固态 2H NMR 测量，使用氘标记材料，我们证明，由于组分间非共价相互作用的强度，互锁支柱烯烃轴的几何形状决定了具有不同独立局部动力学的材料的获得。此外，还通过对苯醌在不同溶剂和温度下的扩散和光释放来测定这些新型铜-轮烷材料作为分子计量容器的有用性。