Molecular Structure, Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine.

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 (HTTDPz and NiTTDPz, respectively). The geometrical and electronic structure of HTTDPz 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 and D symmetry was obtained for HTTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state A, 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 HTTDPz and NiTTDPz were studied experimentally and simulated theoretically.