78786-45-5Relevant academic research and scientific papers
Molecular Pivot-Hinge Installation to Evolve Topology in Rare-Earth Metal–Organic Frameworks
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
, p. 16682 - 16690 (2019)
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.
