Metastable metal imidazolates: development of targeted syntheses by combining experimental and theoretical investigations of the formation mechanisms <jats:title>Abstract</jats:title> <jats:p>In this report, we summarize our experimental and theoretical investigations in the zinc(II) imidazolate, [Zn(im)<jats:sub>2</jats:sub>], and zinc(II) 4,5-dichloroimidazolate, [Zn(dcim)<jats:sub>2</jats:sub>], systems that have been published previously. This comprises a study on the thermodynamic stabilities of the two densest phases with coi and zni framework structures in the [Zn(im)<jats:sub>2</jats:sub>] system including the discovery and characterization of a new [Zn(im)<jats:sub>2</jats:sub>·0.5py]-neb phase (py = pyridine), a study on the mechanism of formation of the [Zn(im)<jats:sub>2</jats:sub>]-zni phase as well as a study on the discovery and characterization of a new [Zn(dcim)<jats:sub>2</jats:sub>]-SOD phase. In addition, we present as yet unpublished work. This concerns the discovery and characterization of a new [Zn(im)<jats:sub>2</jats:sub>·0.5mor]-neb phase (mor = morpholine) and investigations of the mechanisms of crystallization of [Zn(im)<jats:sub>2</jats:sub>·0.5py]-neb and [Zn(im)<jats:sub>2</jats:sub>·0.5mor]-neb as well as an evalutation of time-resolved SAXS/WAXS data recorded <jats:italic>in-situ</jats:italic> during the formation of [Zn(im)<jats:sub>2</jats:sub>]-zni.</jats:p> 229 12 807-822 807-822 Walter de Gruyter GmbH