Ligand Exchange in the Synthesis of Metal-Organic Frameworks Occurs Through Acid-Catalyzed Associative Substitution

研究成果: 雜誌貢獻期刊論文同行評審

20 引文 斯高帕斯(Scopus)

摘要

The syntheses of metal-organic frameworks (MOFs) can be improved through modulated synthesis, synthesis employing precursors, and postsynthetic exchange (PSE) modifications, all of which share ligand exchange as a common and crucial reaction. To date, however, the mechanism of ligand exchange and the underlying principles governing it have remained elusive. Herein, we report energy landscapes for the ligand exchange processes of 1,4-benzenedicarboxylic acid and 2,3,5,6-tetrafluoro-1,4-benzenedicarboxylic acid with Zr6O4(OH)4(OMc)12 (OMc = methacrylate), as calculated using density functional theory (DFT). The rate-limiting step of ligand exchange follows an associative-substitution mechanism catalyzed by protons, consistent with previous kinetic data. Our calculations suggest that the acid catalysis is dependent on the relative basicities of the incoming and outgoing ligands coordinated in the complex, allowing molecular-level rationalization of many seminal MOF syntheses that had previously been interpreted macroscopically. Our results provide new insights for MOF synthesis and new clues for the rational de novo synthesis of MOFs.

原文???core.languages.en_GB???
頁(從 - 到)14457-14466
頁數10
期刊Inorganic Chemistry
58
發行號21
DOIs
出版狀態已出版 - 4 11月 2019

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