Yang Yunhui, Fernández-Seriñán Pilar, Ortín-Rubio Borja, Samanta Partha, Gándara Felipe, Proserpio Davide M, Nam Dongsik, Juanhuix Judith, Imaz Inhar, Maspoch Daniel
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, and Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona 08193, Spain.
Departament de Química, Facultat de Ciències, Universitat Autònoma de Barcelona, Bellaterra 08193, Spain.
J Am Chem Soc. 2025 Jan 8;147(1):1344-1355. doi: 10.1021/jacs.4c15936. Epub 2024 Dec 23.
Herein, we report how merging and clipping nets in metal-organic frameworks (MOFs) can be controlled in a single-crystal-to-single-crystal fashion using three different approaches─the merged net, clip-off chemistry, and linker reinstallation─to design and synthesize three- and two-merged net MOFs. Initially, we show the formation of three isoreticular three-merged net MOFs by linking a trimeric Sc cluster, Sc(μ-Ο)(-COO), with ditopic zigzag and tritopic linkers. The resulting MOFs exhibit three-merged edge-transitive nets─ + + ─for the first time. Then, using these three-merged net MOFs as precursors, we selectively remove one of these subnets, the net, via clip-off chemistry to form two-merged net MOFs. This process involves the cleavage of olefinic groups via ozonolysis, providing the resulting two-merged net MOFs with free carboxylic acid groups that can be used to tune their sorption properties such as the removal of cationic organic pollutants. Finally, we use the linker reinstallation approach to convert the two-merged net MOFs back to the three-merged net MOFs. This approach allows for the postsynthetic addition of the previously removed merged net, enabling recovery of the initial three-merged net MOFs or synthesis of new ones using novel ditopic zigzag linkers.
在此，我们报告了如何使用三种不同的方法——合并网络、切断化学和连接体重新安装，以单晶到单晶的方式控制金属有机框架（MOF）中的合并和切断网络，从而设计和合成三合并网络和二合并网络MOF。首先，我们展示了通过将三聚体Sc簇Sc(μ-Ο)(-COO)与双齿之字形和三齿连接体相连，形成三种同构的三合并网络MOF。所得MOF首次展现出三合并的边传递网络—— + + 。然后，以这些三合并网络MOF为前体，我们通过切断化学选择性地去除其中一个子网，即 网络，以形成二合并网络MOF。此过程涉及通过臭氧分解裂解烯烃基团，为所得的二合并网络MOF提供游离羧酸基团，可用于调节其吸附性能，如去除阳离子有机污染物。最后，我们使用连接体重装方法将二合并网络MOF转换回三合并网络MOF。这种方法允许在合成后添加先前去除的 合并网络，从而恢复初始的三合并网络MOF，或使用新型双齿之字形连接体合成新的MOF。
