Metastable Crystalline Metal Imidazolates; Development of Targeted Syntheses by Combining Experimental and Theoretical Investigations of the Formation Mechanisms

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Owing to the progress made in the first period the work for the second period shall concentrate on metastable crystalline zinc imidazalotes ("Zeolitic Imidazolate Frameworks", ZIFs). The aim of the second period shall be the development of targeted syntheses of new metastable ZlFs with 4,5-disubstituted imidazolate bridging ligands (linkers). A particular, novel aspect of the syntheses shall be the use of simple monotopic ligands that act as modulators on the complex formation equilibria at the zinc cations and the deprotonation equilibria at the imidazole derivative during nucleation (and crystal growth), thereby enabling a selection of the phase to be formed. For synthesis development a detailed mechanistic understanding of the molecular and colloidal formation processes shall be achieved via extensive experimental time-resolved ex-situ and in-situ investigations of the reactions, interpretation of the obtained time-dependent scattering data by application of kinetic models, and theoretical modeling of the nucleation processes with explicit consideration of solvent and modulator molecules. New, potentially existing ZIFs as possible synthesis targets shall be predicted by theoretical methods with recourse to topological databases.