Single-Crystalline UiO-67-Type Porous Network Stable to Boiling Water, Solvent Loss, and Oxidation

Inorg Chem. 2018 Jun 4;57(11):6198-6201. doi: 10.1021/acs.inorgchem.8b00404. Epub 2018 May 21.

Abstract

With methylthio groups flanking the carboxyl groups, the 3,3',5,5'-tetrakis(methylthio)biphenyl dicarboxylate (TMBPD) linker forms a zirconium(IV) carboxylate porous framework featuring the topology of the UiO-67 prototype, i.e., with a face-centered-cubic array of the Zr6O4(OH)4 clusters. Thioether functionalization proves valuable because the ZrTMBPD crystal is found to be exceptionally stable not only upon long-term exposure to air but also in boiling water and a broad range of pH conditions. The hydrophobicity of the metal-organic framework can also be tuned by simple H2O2 oxidation, as illustrated in the water contact-angle measurement of the pristine and H2O2-treated ZrTMBPD solid.