Crystallographic Visualization of Post-synthetic Nickel Clusters into Metal-Organic Framework.

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ID: 4768
2019
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Abstract
Post-synthetic metalation (PSM) has been employed as a robust method for the post-synthetic modification of Metal-Organic Frameworks (MOFs). However, the lack of relevant information that can be obtained for the post-synthetically introduced metallic ions has hindered the development of PSM applications. Thanks to the advancement in single-crystal X-ray diffraction (SCXRD) technology, there have been a few recent examples in which successful post-synthetic introduction of single metal ions into MOFs occurred at the defined chelating sites. These works have provided useful explanations about the complicated host-guest chemistry involved in PSMs. On the other hand, there are no reported examples with crystallographic snapshots of the post-synthetic installation of metal clusters into the pores of MOFs using an ordinary SCXRD due to the loss of crystallinity of parent matrix during the PSM process. Herein, by the careful selection of starting materials and controlling the reaction conditions, we report the first crystallographic visualization of metal clusters inserted into Zr-based MOFs via PSM. The structural advantages of the parent Zr-MOF, which are inherited from the stable Zr6 cluster and triazole-containing dicarboxylate ligand, ensure both the preservation of high crystallinity and the presence of flexible coordination sites for PSM. Furthermore, PSM of metal clusters in a MOF pore space enhances stability of the final samples while also imparting the functionality of a successful catalyst toward ethylene dimerization reaction. The related construction ideas and structural information detailed in this work can help lay the foundation for further advancements using the post-modification of MOFs as well as open new doors for the utilization of SCXRD technology in the field of MOFs.
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Authors Wang, Xiao-Ning;Zhang, Peng;Kirchon, Angelo;Li, Jialuo;Chen, Wen-Miao;Zhao, Yu-Meng;Li, Bao;Zhou, Hong-Cai;
Journal Journal of the American Chemical Society
Year 2019
DOI
10.1021/jacs.9b06711
URL
Keywords Keywords not found

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