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Molecular Pivot‐Hinge Installation to Evolve Topology in Rare‐Earth Metal–Organic Frameworks
Author(s) -
Feng Liang,
Wang Yutong,
Zhang Kai,
Wang KunYu,
Fan Weidong,
Wang Xiaokang,
Powell Joshua A.,
Guo Bingbing,
Dai Fangna,
Zhang Liangliang,
Wang Rongming,
Sun Daofeng,
Zhou HongCai
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201910717
Subject(s) - linker , topology (electrical circuits) , desymmetrization , stacking , steric effects , cluster (spacecraft) , metal organic framework , chemistry , crystallography , materials science , combinatorial chemistry , stereochemistry , catalysis , enantioselective synthesis , computer science , organic chemistry , combinatorics , mathematics , adsorption , programming language , operating system
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‐SO 2 with C 2 v symmetry and 12‐connected RE 9 clusters leads to the formation of a fascinating (4,12)‐c dfs new topology. Interestingly, when replacing L‐SO 2 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‐(CH 3 ) 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‐SO 2 allows for efficient cascade catalytic transformation within the functionalized channels.