Dynamic Coordination Chemistry of Fluorinated Zr-MOFs: Synthetic Control and Reassembly/Disassembly Beyond de Novo Synthesis to Tune the Structure and Property.
Known for excellent stability, porosity and functionality, the high-valent Zr4+ metal-organic frameworks (Zr-MOFs) still meets synthetic challenge in modulating the strength of Zr-Ocarboxylate linkage. Herein we explore the unusual coordination dynamics of fluorinated Zr-MOFs by designing two trifluoromethyl modified ligands with distinct geometry preference to form a family of thermodynamic and kinetic products. The low-connecting kinetic Zr-MOFs possess substitutable coordination sites to endow Zr6 -cluster with extra dynamic behaviors, thus opening a post-synthetic pathway to sequential reassembly/disassembly processes. Comprehensive factors, including ligand geometry, Zr6 -cluster connectivity, acid modulator and reaction temperature/concentration, have been studied for controllable syntheses. The stability, hydrophobicity and gas adsorption/separation properties of obtained Zr-MOFs are explored. This work sheds light on the understanding of the dynamic coordination chemistry of Zr-MOFs beyond strong Zr-O bond, which poses a versatile platform for modification and functionalization of Zr-MOFs.
['Chen|Cheng-Xia|CX|', 'Fan|Yan-Zhong|YZ|', 'Cao|Chen-Chen|CC|', 'Wang|Hai-Ping|HP|', 'Fan|Ya-Nan|YN|', 'Jiang|Ji-Jun|JJ|', 'Wei|Zhang-Wen|ZW|', 'Maurin|Guillaume|G|', 'Su|Cheng-Yong|CY|http://orcid.org/0000-0003-3604-7858']
dynamics fluorine metal-organic frameworks post-synthesis