Lim Jaewoong, Lee Seonghwan, Ha Hyeonbin, Seong Junmo, Jeong Seok, Kim Min, Baek Seung Bin, Lah Myoung Soo
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.
Department of Chemistry, Chungbuk National University, Cheongju, 28644, Republic of Korea.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9296-9300. doi: 10.1002/anie.202100456. Epub 2021 Mar 5.
MOF-74 is one of the most explored metal-organic frameworks (MOFs), but its functionalization is limited to the dative post-synthetic modification (PSM) of the monodentate solvent site. Owing to the nature of the organic ligand and framework structure of MOF-74, the covalent PSM of MOF-74 is very demanding. Herein, we report, for the first time, the covalent PSM of amine-tagged defective Ni-MOF-74, which is prepared by de novo solvothermal synthesis by using aminosalicylic acid as a functionalized fragmented organic ligand. The covalent PSM of the amino group generates metal binding sites, and subsequent post-synthetic metalation with Pd ions affords the Pd -incorporated Ni-MOF-74 catalyst. This catalyst exhibits highly efficient, size-selective, and recyclable catalytic activity for the Suzuki-Miyaura cross-coupling reaction. This strategy is also useful for the covalent modification of amine-tagged defective Ni (DOBPDC), an expanded analogue of MOF-74.
MOF-74是研究最为深入的金属有机框架材料（MOF）之一，但其功能化仅限于单齿溶剂位点的配位后合成修饰（PSM）。由于MOF-74的有机配体性质和框架结构，MOF-74的共价PSM要求非常高。在此，我们首次报道了胺标记的缺陷型Ni-MOF-74的共价PSM，它是通过使用氨基水杨酸作为功能化片段有机配体的从头溶剂热合成法制备的。氨基的共价PSM产生金属结合位点，随后用Pd离子进行后合成金属化，得到掺入Pd的Ni-MOF-74催化剂。该催化剂对铃木-宫浦交叉偶联反应表现出高效、尺寸选择性和可回收的催化活性。该策略对于胺标记的缺陷型Ni（DOBPDC）（MOF-74的扩展类似物）的共价修饰也很有用。
