We report the synthesis and characterization of porphyrin containing metal–organic frameworks that show high metal tunability without altering the framework topology.

Ni(OAc)₂–H₃BTC system in various ionic liquids, [RMI]X (R = ethyl, n-propyl, n-butyl; X = Cl, Br, I), produced five MOFs in two structure types; their relative thermodynamic stability varies with the size of RMI⁺, and the X⁻ ions govern the kinetic factors so that their combination effects determine the final product.

A novel metal–organic framework, [(Co(cis-ZnDCPP)(bpy)]·4DMF·H₂O (cis-ZnDCPP = zinc 5,10-di(4-carboxyphenyl)-15,20-diphenylporphyrin; bpy = 4,4′-bipyridine; DMF = dimethyl formamide), has been synthesized from the solvothermal reaction and exhibits unique CdI₂ layers constructed from paddle-wheel buiding units, Co₂(COO)₄, cis-ZnDCPP, and 4,4′-bipyridine linker.