In:
Chemistry – A European Journal, Wiley, Vol. 26, No. 37 ( 2020-07-02), p. 8254-8261
Abstract:
Known for excellent stability, porosity and functionality, the high‐valent Zr 4+ metal–organic frameworks (Zr‐MOFs) still meets synthetic challenge in modulating the strength of Zr‐O carboxylate 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 Zr 6 ‐cluster with extra dynamic behaviors, thus opening a post‐synthetic pathway to sequential reassembly/disassembly processes. Comprehensive factors, including ligand geometry, Zr 6 ‐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.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.202001052
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
1478547-X