Modulated Synthesis of Metal‐Organic Frameworks through Tuning of the Initial Oxidation State of the Metal
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© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Modulated solvothermal synthesis and other alterations of synthetic conditions have been used to control metal-organic framework (MOF) crystallinity, porosity, and other properties. However, so far these changes have mostly been limited to changes in solvent, pH, or modulating acid type or concentration. In this work, we introduce a new method for the tuning of MOF synthesis: modulation through alteration of the metal source's initial oxidation state. By choosing a metal source that should be reduced or oxidized at high temperature in the solvent, metal concentration can be started at zero for initially insoluble starting materials and then increased as the metal reacts with the solvent, slowing and altering crystallization compared to standard MOF solvothermal synthesis. This concept is demonstrated through the synthesis of PCN-47, PCN-48, and PCN-49, MOFs with distinct structures and porosities synthesized from the same metal and ligand with the metal initially in different oxidation states.
author list (cited authors)
Bosch, M., Sun, X., Yuan, S., Chen, Y., Wang, Q. i., Wang, X., & Zhou, H.