Pore surface engineering in a zirconium metal–organic framework via thiol-ene reaction

• A porous olefin-functionalized Zr(IV)-based metal–organic framework has been constructed.
• The surface of olefin-functionalized Zr-MOF could be decorated with organic molecules via thiol-ene reaction.
• The crystallinity and permanent porosity of the framework were maintained during the post-synthetic modification process.

A porous olefin-functionalized Zr(IV)-based metal–organic framework, denoted as UiO-68-allyl, has been constructed. Our results clearly demonstrated that the surface of UiO-68-allyl could be decorated with organic molecule (ethanethiol) via thiol-ene reaction. More importantly, the crystallinity of the framework were maintained during the post-synthetic modification process. However, the microporosity of the framework is retained but the surface area decreased, due to the grafting of ethylthio groups into the pores. From our studies, we can conclude that the strategy of post-synthetic modification of UiO-68-allyl via thiol-ene reaction may be general. Furthermore, we may anchor other desired functional group onto the pore walls in Zr-MOFs via thiol-ene reaction, enabling more potential applications.

graphical abstractIn this manuscript, we reported the post-synthetic modification of an olefin-functionalized Zr(IV)-based metal–organic framework via thiol-ene reaction.Figure optionsDownload as PowerPoint slide