We can draw the following conclusions from this computational study: (a) The inclusion of implicit solvation (via dielectric embedding methods) is required to achieve chemically sound structures as opposed to in vacuo calculations. Explicit solvation is only needed if accurate energy barriers are to be calculated, but the energies of equilibrium structures do not seem to depend much on the inclusion of explicit solvent or counterions, (b) The most stable cluster (free energy of formation per Zn atom of -4.85 eV) in the initial process of cluster growth is ZnIm 4 , although clusters such as ZnIm 3 , Zn 2 Im 7 , Zn 2 Im 7 , Zn 3 Im 9 , Zn 3 Im 10 , or Zn 4 Im 12 do have energies close to -4.50 eV, and would therefore be present in solution at appreciable quantities. All these species, except ZnIm 3 , have a tetrahedrally coordinated Zn 2+ cation, (c) Zn x Im y clusters take longer than Zn x mIm y to be optimized, due to the shallower nature of their potential energy surfaces, which is related to the higher constraints induced by the larger sizes of the mIm groups, (d) The low porosity zni structure, which is the most stable crystal formed with Im -ligands, is less stable than the SOD structure of ZIF-8 when the Zn 2+ cations are connected with mIm -ligands. This might be due the presence of larger pores in SOD, which allow for rotation of the mIm -ligands to point their methyl groups into different places, thus avoiding close contacts. (e) The ZnIm 4 cluster is the most stable cluster determined for a wide range of sizes, and clusters do not start becoming more stable than this cluster until they have more than 40 Zn atoms, which suggests that the smaller clusters would not have long lifespans, since they are likely to undergo formation and dissolution processes to yield stable ZnIm 4 clusters, (f) Ostwald's rule of stages seems to be observed, as glassy clusters are formed before crystalline clusters become more stable. The crystal structures formed in the nucleation process are then determined by the kinetic factors that the synthesis conditions create, permitting the transformation of the glassy particles to crystalline particles.