Functionalization of Magnetic UiO-66-NH2 with a Chiral Cu(l-proline)2 Complex as a Hybrid Asymmetric Catalyst for CO2 Conversion into Cyclic Carbonates.

Abstract

In this study, a chiral [Cu(l-proline)2] complex-modified Fe3O4@SiO2@UiO-66-NH2(Zr) metal-organic framework [Fe3O4@SiO2@UiO-66-NH-Cu(l-proline)2] via multifunctionalization strategies was designed and synthesized. One simple approach to chiralize an achiral MOF-structure that cannot be directly chiralized using a chiral secondary agent like 4-hydroxy-l-proline. Therefore, this chiral catalyst was synthesized with a simple and multistep method. Accordingly, Fe3O4@SiO2@UiO-66-NH2 has been synthesized via Fe3O4 modification with tetraethyl orthosilicate and subsequently with ZrCl4 and 2-aminoterephthalic acid. The presence of the silica layer helps to stabilize the Fe3O4 core, while the bonding between Zr4+ and the -OH groups in the silica layer promotes the development of Zr-MOFs on the Fe3O4 surface, and then the surfaces of the synthesized magnetic MOFs composite are functionalized with 1,2-dichloroethane and Cu(II) complex with 4-hydroxy-l-proline, [Cu(l-proline)2] to afford the magnetically chiral nanocatalyst. Multiple techniques were employed to characterize this magnetically chiral nanocatalyst such as Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX), powder X-ray diffraction (PXRD), circular dichroism (CD), inductively coupled plasma (ICP), thermogravimetric analysis (TGA), vibrating-sample magnetometry (VSM), and Brunauer-Emmett-Teller (BET) analyses. Moreover, a magnetically chiral nanocatalyst shows the asymmetric CO2 fixation reaction under solvent-free conditions at 80 °C and in ethanol under reflux conditions with up to 99 and 98% ee, respectively. Furthermore, the reaction mechanism was illustrated concerning the total energy of the reactant, intermediates and product, and the structural parameters were analyzed.