Controlled construction of metal-organic frameworks: Hydrothermal synthesis, X-ray structure, and heterogeneous catalytic study

Abstract

The role of pH in the formation of metal-organic frameworks (MOFs) has been studied for a series of magnesium-based carboxylate framework systems. Our investigations have revealed the formation of five different zero-dimensional (0D) to three-dimensional (3D) ordered frameworks from the same reaction mixture, merely by varying the pH of the medium. The compounds were synthesized by the hydrothermal method and characterized by single-crystal X-ray diffraction. Increase of the pH of the medium led to abstraction of the imine hydrogen from the ligand and a concomitant increase in the OH- ion concentration in the solution, facilitating the construction of higher dimensional framework compounds. A stepwise increase in pH resulted in a stepwise increase in the dimensionality of the network, ultimately leading to the formation of a 3D porous solid. A gas adsorption study of the 3D framework compound confirmed its microporosity with a BET surface area of approximately 450 m2 g-1. Notably, the 3D framework compound catalyzes aldol condensation reactions of various aromatic aldehydes with acetone under heterogeneous conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.