Analyzing Stabilities of Metal-Organic Frameworks: Correlation of Stability with Node Coordination to Linkers and Degree of Node Metal Hydrolysis.

Among the important properties of metal-organic frameworks (MOFs) is stability, which may limit applications, for example, in separations and catalysis. Many MOFs consist of metal oxo cluster nodes connected by carboxylate linkers. Addressing MOF stability, we highlight connections between metal oxo cluster chemistry and MOF node chemistry, including results characterizing Keggin ions and biological clusters. MOF syntheses yield diverse metal oxo cluster node structures, with varying numbers of metal atoms (3-13) and the tendency to form chains. MOF stabilities reflect a balance between the number of node-linker connections and the degree of node hydrolysis. We summarize literature results showing how MOF stability (the temperature of decomposition in air) depends on the degree of hydrolysis/condensation of the node metals, which is correlated to their degree of substitution with linkers. We suggest that this correlation may help guide the discovery of stable new MOFs, and we foresee opportunities for progress in MOF chemistry emerging from progress in metal oxo cluster chemistry.