Iron species supported on a mesoporous zirconium metal-organic framework for visible light driven synthesis of quinazolin-4(3H)-ones through one-pot three-step tandem reaction.

A bioinspired iron(III)porphyrinic Zr-MOF, PCN-222(Fe), was modified by post-synthetic cluster metalation with iron(III) chloride, as a cheap, earth-abundant, and environmentally friendly metal precursor, towards formation a new multifunctional MOF, namely Fe@PCN-222(Fe). The MOF consists of bimetallic (Zr-oxo-Fe) nodes linked by Fe(III)porphyrin struts. The cluster metalation and pre-activation treatment of PCN-222(Fe) were performed cooperatively using the FeCl3. The respective MOF was characterized through various techniques, such as FT-IR, PXRD, ICP-AES, BET surface area, SEM, UV-Vis DRS, TGA/DSC, PL, and XPS analyses. The solid showed catalytic activity for one-pot tandem synthesis of quinazolin-4(3H)-ones from alcohols and 2-aminobenzamide through a three-consecutive-step reaction (oxidation-cyclization-oxidation) under visible light irradiation using air or oxygen without adding any additive. In addition, its catalytic performance was superior to that of the bare PCN-222(Fe) and the corresponding homogeneous catalysts. The experiments indicate that the solid MOF acts as both a photoredox and Lewis acid catalyst. Hot-filtration and Fe-leaching tests as well as reusability experiments confirm that the nominal MOF acts as an efficient reusable heterogeneous catalyst for at least three runs without significant decrease in its activity. This work demonstrates the potential of using MOFs as supports for single-site metal species towards preparation of multifunctional MOFs for modern organic transformations combining photocatalysis and catalysis.