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Angew Chem Int Ed Engl. 2019 Sep 13. doi: 10.1002/anie.201910717. [Epub ahead of print]

Molecular Pivot-Hinge Installation to Evolve Topology in Rare-Earth Metal-Organic Frameworks.

Author information

1
Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
2
College of Science, School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao, Shandong, 266580, China.
3
Xi'an Institute of Flexible Electronics, Northwestern Polytechnical University, Xi'an, 710072, China.
4
Department of Materials Science and Engineering, Texas A&M University, College Station, Texas, 77843-3003, USA.

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 C2v 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.

KEYWORDS:

heterogeneous catalysis; linker desymmetrization; metal-organic frameworks; structural evolution; topology

PMID:
31518476
DOI:
10.1002/anie.201910717

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