(22H,24H)-5,10,15,20-Tetraazaporphin and its perfluorosubstituted: Quantum-chemical design by using various DFT model chemistries

Using two variants of DFT model chemistries, specifically M06/def2TZVP and B3PW91/TZVP combined with D3 Grimme dispersion, the molecular structures of hydrogenated porphyrazine and its octafluoro-substituted derivatives, namely (22H,24H)-5,10,15,20-tetraazaporphin and perfluoro-(22H,24H)-5,10,15,20-tetraazaporphin, were calculated. The key bond lengths, valence and non-bonded angles in these compounds, along with NBO analysis data, are presented. It is observed that each of these compounds features groups of four nitrogen atoms that are strictly planar; additionally, the four nitrogen atoms not bonded to hydrogen are positioned at the vertices of a square, while those forming N–H bonds are at the vertices of a rhombus. The 16-membered macrocycles in all these compounds are non-planar, although their deviation from coplanarity generally does not exceed [Formula: see text]. According to NBO analysis, there is a high degree of electron density delocalization within these compounds. The standard enthalpy of formation ([Formula: see text], standard entropy ([Formula: see text], and standard Gibbs free energy ([Formula: see text] were also calculated. It was found that in perfluoro-(22H,24H)-5,10,15,20-tetraazaporphin, unlike (22H,24H)-5,10,15,20-tetraazaporphin, the values of [Formula: see text] and [Formula: see text] are negative, indicating significantly greater thermodynamic stability compared to (22H,24H)porphyrazine. Good agreement was noted between the data derived from the two DFT model chemistry methods.