Lerma-Berlanga Belén, Ganivet Carolina R, Almora-Barrios Neyvis, Vismara Rebecca, Navarro Jorge A R, Tatay Sergio, Padial Natalia M, Martí-Gastaldo Carlos
Functional Inorganic Materials Team, Instituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán-2, 46980, Paterna, Spain.
Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain.
Angew Chem Int Ed Engl. 2022 Oct 10;61(41):e202208139. doi: 10.1002/anie.202208139. Epub 2022 Sep 5.
The value of covalent post-synthetic modification in expanding the chemistry and pore versatility of reticular solids is well documented. Here we use mesoporous crystals of the metal-organic framework (MOF) UiO-68-TZDC to demonstrate the value of tetrazine connectors for all-purpose inverse electron-demand Diels-Alder ligation chemistry. Our results suggest a positive effect of tetrazine reticulation over its reactivity for quantitative one-step functionalization with a broad scope of alkene or alkyne dienophiles into pyridazine and dihydropyridazine frameworks. This permits generating multiple pore environments with diverse chemical functionalities and the expected accessible porosities, that is also extended to the synthesis of crystalline fulleretic materials by covalent conjugation of fullerene molecules.
共价合成后修饰在扩展网状固体的化学性质和孔隙多样性方面的价值已有充分记载。在此，我们使用金属有机框架（MOF）UiO - 68 - TZDC的介孔晶体来证明四嗪连接体对于通用的逆电子需求狄尔斯 - 阿尔德环加成连接化学的价值。我们的结果表明，四嗪网状结构对其与多种烯烃或炔烃亲双烯体进行定量一步功能化反应生成哒嗪和二氢哒嗪框架的反应活性具有积极影响。这使得能够生成具有多种化学功能和预期可及孔隙率的多个孔隙环境，并且这种方法还扩展到通过富勒烯分子的共价共轭来合成结晶富勒烯材料。
