Post‐Synthetic Modification of a 1D Mixed‐Linker Zn(II) Coordination Polymer for Acid‐Catalyzed Alcoholysis of Epoxides

Abstract

Rational design of heterogeneous acid catalysts possessing uniform dispersion of active sites plays a significant role in the catalytic performance. In the present work, a coordination polymer, [Zn(4,4'‐bpy)(μ‐Hbtc)(H2O)] ⋅ 2H2O (Zn‐CP), was solvothermally synthesized using 4,4'‐bpy (=4,4'‐bipyridine) and H3btc (=1,3,5‐benzenetricarboxylic acid) mixed linkers. Single crystal X‐ray analysis of the polymer displayed that Zn‐CP chains were decorated with 4,4'‐bpy having unidentate coordination fashion. Then, the free N atom of the linker in Zn‐CP was functionalized by ‐SO3H groups to afford Zn‐CP‐SO3H with enhanced acidity. The structures were characterized by FT‐IR, thermogravimetric analysis, powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), temperature programmed desorption of NH3 (NH3‐TPD), and field emission scanning electron microscopy (FE‐SEM) analyses. The coordination polymer was employed as a heterogeneous catalyst for the alcoholysis of epoxides under room conditions. Zn‐CP‐SO3H exhibited excellent catalytic activity and regioselectivity in the methanolysis of styrene oxide within short reaction time.