J Am Chem Soc. 2019 Feb 6;141(5):2161-2168. doi: 10.1021/jacs.8b13502. Epub 2019 Jan 25.
We introduce the concept of domain building blocks (DBBs) as an effective approach to increasing the diversity and complexity of metal-organic frameworks (MOFs). DBBs are defined as distinct structural or compositional regions within a MOF material. Using the DBB approach, we illustrate how an immense number of multivariate MOF materials can be prepared from a small collection of molecular building blocks comprising the distinct domains. The multivariate nature of the MOFs is determined by the sequence of DBBs within the MOF. We then apply this approach to the construction of a rich library of UiO-67 stratified MOF (sMOF) particles consisting of multiple concentric DBBs. We discuss and highlight the negative consequences of linker exchange reactions on the compositional integrity of DBBs in the UiO-67 sMOFs and propose and demonstrate mitigation strategies. We also demonstrate that individual strata can be specifically postsynthetically addressed and manipulated. Finally, we demonstrate the versatility of these synthetic strategies through the preparation of sMOF-nanoparticle composite materials.
我们引入了“结构基块”（domain building blocks，DBBs）的概念，作为增加金属有机骨架（MOFs）多样性和复杂性的有效方法。DBBs 被定义为 MOF 材料中具有明显结构或组成的区域。使用 DBB 方法，我们说明了如何从包含不同结构域的少量分子构建块中制备出大量多元 MOF 材料。MOFs 的多元性取决于 MOF 中 DBB 的顺序。然后，我们将该方法应用于构建由多个同心 DBB 组成的 UiO-67 分层 MOF（sMOF）颗粒的丰富库。我们讨论并强调了配体交换反应对 UiO-67 sMOF 中 DBB 组成完整性的负面影响，并提出并证明了缓解策略。我们还证明可以对各个层进行特定的后合成处理和操作。最后，我们通过制备 sMOF-纳米颗粒复合材料展示了这些合成策略的多功能性。
