MOF nano porous-supported C-S cross coupling through one-pot post-synthetic modification

Abstract

UIO-66-NH2-Fu@Ni has been synthesized by anchoring a molecular nickel furfural (Fu) complex into a functionalized nanoporous metal-organic framework (MOF) with the amine functional groups, using the one-pot post-synthetic modification. This new catalyst was identified via Fourier-transform infrared (FT-IR) spectroscopy, proton-nuclear-magnetic-resonance (1HNMR) spectroscopy, nitrogen gas adsorption-desorption method, thermogravimetric analyses (TGA), energy-dispersive X-ray- mapping spectroscopy (EDX-MAP), field emission scanning electron microscopy (FE-SEM), and X-ray diffraction (XRD). 1HNMR analysis showed that around 16% of the amine functional groups of the nanocrystalline UIO-66-NH2 framework were modified with nickel complex. Also, according to the inductive couple plasma atomic emission spectroscopy (ICP), around 2.98 w% of Ni was determined in the modified MOF. The Ni complex which was supported by UIO-66-NH2 nanocatalyst was effectively used as a heterogeneous catalyst for the formation of sulfur-containing molecules such as thioethers which are generally found in chemical biology, organic synthesis, and materials chemistry through the C-S bond cross-coupling of aryl iodides with thiols. UIO-66-NH2-Fu@Ni propagated the condensation reaction by different aryl iodides and aryl thiols in moderate conditions in the presence of K2CO3 as a base in high reaction yield during 8–14 h. The Ni complex which was supported by UIO-66-NH2 nanocatalyst was simply recycled and reused thrice while its catalytic activity was maintained approximately.