Heteroligand macrotetracyclic complexes of 3d elements with phthalocyanine and two fluoride anions: molecular structures and thermodynamic parameters, as determined from DFT calculations

Molecular structure calculations of heteroligand macrotetracyclic complexes of 3d elements M IV (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu) with phthalocyanine as the (NNNN) donor-atom ligand and two fluoride anions were carried out in terms of the density functional theory with the OPBE functional and the TZVP basis set. The key bond lengths, bond angles, and non-bond angles in the complexes are presented. The standard enthalpies, entropies, and Gibbs energies of formation of the compounds are calculated. According to calculations, all complexes have tetragonal bipyramidal or similar structures. The complex-forming agent M IV lies in the plane formed by the donor nitrogen atoms of the phthalocyanine ligand. The M-N bond lengths as well as the M-F bond lengths are equal to one another. All six-membered metal chelate rings in the complexes are identical to one another both in terms of the sum and the set of the bond angles. The same holds for the five-membered rings containing nitrogen atoms.