Expanding the Horizon of Multicomponent Oxidative Coupling Reaction via the Design of a Unique, 3D Copper Isophthalate MOF-Based Catalyst Decorated with Mixed Spinel CoFe2O4 Nanoparticles

This work discloses the first ever magnetically retrievable copper isophthalate-based metal-organic framework (MOF) decorated with surface-modified cobalt ferrite (CoFe2O4) nanoparticles that have been utilized as catalytic reactors for obtaining a relatively large number of biologically active benzimidazole scaffolds. A facile one-pot solvothermal approach was employed for obtaining spherical and monodisperse CoFe2O4 nanoparticles, which were subsequently modified using suitable protecting and functionalizing agents. Finally, these functionalized magnetic nanoparticles were anchored onto the three-dimensional copper isophthalate MOF via a covalent immobilization methodology. The exploitation of advanced microscopic tools such as transmission electron microscopy and scanning electron microscopy provided valuable insights into the morphology of the immobilized MOF. These results indicated that the surface-modified magnetic nanoparticles had grown onto the surface of copper-5-nitroisophthalic acid MOF. A greener C-H functionalization strategy that involves the multicomponent oxidative cross-coupling between two different set of amines (sp(2)-hybridized nitrogen-containing anilines and sp(3)-hybridized nitrogen-containing alkyl/aryl amine derivatives) and sodium azide has been incorporated to provide access to a broad spectrum of the value-added target benzimidazole moieties. It is interesting to note that this magnetic MOF-catalyzed protocol not only replaces toxic solvents with water, which is a green solvent, but also enhances the economic competitiveness since the magnetic catalyst can be readily recovered and recycled for eight consecutive runs.