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

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.