3D-ELEMENT COORDINATION COMPOUNDS WITH SUBPHTHALOCYANINE: QUANTUM-CHEMICAL CALCULATION BY USING DFT

Using the data of quantum chemical calculations obtained by the DFT model chemistries with the M06/TZVP, B3PW91/TZVP, and OPBE/TZVP levels, the possibility of the existence of (666)macrotricyclic complexes, each of which contains a doubly deprotonated form of subphthalocyanine (H2SPc) in the inner coordination sphere with the 3d-element ion ratio M(II) : SPc2- = 1:1, has been shown. The main geometric parameters of the molecular structures of these coordination compounds are presented; it is noted that the chelate MN3 node have a trigonal-pyramidal structure and a very significant (in most cases, more than 90°) deviation from coplanarity. The 6-membered metal chelate and 5-membered non-chelate rings in these complexes are also not planar, but their deviation from coplanarity is much smaller and does not exceed 20° and 5°, respectively. It is noted that all these complexes can be divided into two groups, in the first of which (M = Ti, V, Mn, Co, Ni, Cu, Zn) all M-N bond lengths, valence angles (NMN) in the chelate unit MN3 and non-valence angles between nitrogen atoms included in the chelate unit are practically identical, and in the second (M = Cr, Fe) they differ from each other. Good agreement between the structural data obtained using the three above-mentioned DFT method variants is established, both qualitatively and quantitatively. NBO analysis data for these complexes are presented; it is noted that according to each of the DFT methods used, the ground state of each of the complexes under consideration has the same spin multiplicity as the ground state of the corresponding central ion M(II). The standard thermodynamic parameters of formation (standard enthalpy DfH0, entropy Sf0 and Gibbs energy DfG0) for these metal macrocyclic compounds were also calculated .