Novel bi-elemental “nitrogen-rich” zinc compound—macrocyclic complex with dodecaazacyclododecatetraene-1,4,7,10: design using various versions of density functional theory

Using quantum chemical design within the framework of density functional theory in three versions, namely DFT M06/TZVP, DFT B3PW91/TZVP, and DFT OPBE/TZVP, the possibility of the existence of a new “nitrogen-rich” zinc chemical compound—dodecaazacyclododecatetraene-1,4,7,10, which contains the currently maximum number of nitrogen atoms per one zinc atom, equal to 12, was shown. Data on the structural parameters of this unusual compound and the macrocyclic ligand H₄(N₁₂), of which this compound is a derivative are presented. It was noted that the group of four nitrogen atoms bonded with a zinc atom, and group containing the same atoms in the H₄N₁₂ molecule, are non-coplanar with a relatively small amount in the case of ZnN₁₂ (no more than 6°) and at the same time quite noticeable in the case of H₄(N₁₂) (about 23°) deviation from the plane; , . The nitrogen atoms forming a 12-membered macrocycle are generally not equivalent to each other; it has rather considerable deviation of N12 group from coplanarity (more than 60°). Good agreement was noted between the parameters of molecular structures of ZnN₁₂ and H₄N₁₂ calculated using these various DFT versions. Standard thermodynamic parameters, NBO analysis data, and HOMO/LUMO images for this compound are also presented.