Amine‐Tagged Fragmented Ligand Installation for Covalent Modification of MOF‐74. Issue 17 (5th March 2021)

• Record Type: Journal Article
• Authors: Lim, Jaewoong; Lee, Seonghwan; Ha, Hyeonbin; Seong, Junmo; Jeong, Seok; Kim, Min; Baek, Seung Bin; Lah, Myoung Soo
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 17(2021)
• Page Start: 9296
• Page End: 9300
• Publication Date: 2021-03-05
• Subjects: covalent modification -- fragmented ligands -- heterogeneous catalysis -- metal-organic frameworks -- post-synthetic modification; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202100456
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 II ions affords the Pd II ‐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 Ni2 (DOBPDC), an expanded analogue of MOF‐74. Abstract : Aminosalicylic acid has been used as a functionalized fragment to generate an amine‐tagged defect‐engineered Ni‐MOF‐74, which could be covalently modified post‐synthetically to generate metal‐binding sites. Subsequent metalation with Pd II ions afforded Pd II ‐incorporated Ni‐MOF‐74, which is a highly efficient, size‐selective, and recyclable catalyst for the Suzuki–Miyaura cross‐coupling reaction.