Electronic and geometric structures of metal-free, Al, Ga and In complexes with tetrapyrazinoporphyrazine (TPyzPA) and octachlorotetrapyrazinoporphyrazine (TPyzPACl₈) were investigated by density functional theory (DFT) calculations and compared in order to study the effect of chlorination on the structure and properties of these macrocycles. The nature of the bonds between metal atoms and nitrogen atoms was described using the NBO-analysis. Simulation and interpretation of electronic spectra were performed with the use of time-dependent density functional theory (TDDFT). A description of calculated IR spectra was carried out based on the analysis of the distribution of the potential energy of normal vibrational coordinates.

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically.

Perchlorinated vanadyl tetrapyrazinoporphyrazine (Cl ₈ TPyzPzVO) was synthesized. Redox and spectral properties of Cl ₈ TPyzPzVO were studied in solution. Crystalline ring-reduced dianionic complex was isolated and characterized.

Complexes of tetrabenzoporphyrin (TBP) with vanadyl and titanyl were prepared by complexation directly from metal free H₂TBP. They were characterized using spectral and electrochemical methods and peculiarities of their molecular and electronic structure were investigated by DFT calculations. Properties of MTBP complexes were compared with corresponding complexes of meso- and b-substituted porphyrins, porphyrazines and phthalocyanines. It is shown that fusion of benzene rings strongly facilitates the oxidation process which occurs at +0.3 V, what is much easier than in the case of the corresponding porphyrins (by 0.4 - 0.5 V) and phthalocyanines (by 0.5-0.7 V). At the same time the reduction of tetrabenzoporhyrin complexes is observed at similar potentials as in the case of meso-aryl and b-alkyl substituted porphyrins (0.9-1.2 V), and by 0.4-0.6 V more difficult than in the case of phthalocyanine complexes. The obtained data evidence that VO and TiO complexes of tetrabenzoporphyrins can be used as donors in organic electronics.