Molecular Pivot‐Hinge Installation to Evolve Topology in Rare‐Earth Metal–Organic Frameworks. Issue 46 (30th September 2019)

• Record Type: Journal Article
• Authors: Feng, Liang; Wang, Yutong; Zhang, Kai; Wang, Kun‐Yu; Fan, Weidong; Wang, Xiaokang; Powell, Joshua A.; Guo, Bingbing; Dai, Fangna; Zhang, Liangliang; Wang, Rongming; Sun, Daofeng; Zhou, Hong‐Cai
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 46(2019)
• Page Start: 16682
• Page End: 16690
• Publication Date: 2019-09-30
• Subjects: heterogeneous catalysis -- linker desymmetrization -- metal–organic frameworks -- structural evolution -- topology; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201910717
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Linker desymmetrization has been witnessed as a powerful design strategy for the discovery of highly connected metal–organic frameworks (MOFs) with unprecedented topologies. Herein, we introduce molecular pivot‐hinge installation as a linker desymmetrization strategy to evolve the topology of highly connected rare‐earth (RE) MOFs, where a pivot group is placed in the center of a linker similar to a hinge. By tuning the composition of pivot groups and steric hindrances of the substituents on various linker rotamers, MOFs with various topologies can be obtained. The combination of L‐SO2 with C 2 v symmetry and 12‐connected RE9 clusters leads to the formation of a fascinating (4, 12)‐c dfs new topology. Interestingly, when replacing L‐SO2 with a tetrahedra linker L‐O, the stacking behaviors of RE‐organic layers switch from an eclipsed mode to a staggered stacking mode, leading to the discovery of an intriguing hjz topology. Additionally, the combination of the RE cluster and a linker [(L‐(CH3 )6 )] with more bulky groups gives rise to a flu topology with a new 8‐c inorganic cluster. The diversity of these RE‐MOFs was further enhanced through post‐synthetic installation of linkers with various functional groups. Functionalization of each linker with acidic and basic units in the mesoporous RE‐based PCN‐905‐SO2 allows for efficient cascade catalytic transformation within the functionalized channels. Abstract : Molecular pivot‐hinge installation is introduced as a linker desymmetrization strategy to evolve the topology of rare‐earth metal–organic frameworks (MOFs), where a pivot group is placed in the center of a linker similar to a hinge. By tuning the composition of pivot groups and steric hindrances of the substituents on various linker rotamers, MOFs with various topologies can be obtained.