The molecular structures of gaseous zinc tetrakis (1,2,5-thiadiazolo)porphyrazine, [ZnTTDPz],and 1,2, C 4

Структура молекулы трис-ацетилацетоната железа, Fe(acac)3, была определена в рамках синхронного электронографического/масс-спектрометрического эксперимента, а также с помощью квантово-химических расчетов методом DFT/UB3LYP/cc-pVTZ. Наилучшее согласие между рассчитанными и экспериментальными функциями интен-сивности рассеяния электронов было достигнуто для модели молекулы симметрии D3 с высокоспиновым электронным состоянием. DFT расчеты также указывают на высоко-спиновое электронное состояние 6 A1 как основное при равновесной геометрической кон-фигурации молекулы D3 симметрии.Ключевые слова: трис(ацетилацетонат) железа, спиновое состояние, молекулярная структура, дифракция электронов

By DFT method with B3LYP, PBE, CAM-B3LYP, and B97D functionals, it was found that the molecule 4-(4-tritylphenoxy)phthalonitrile (TPPN) has four conformers. The geometric structure, vibrational frequencies, electronic characteristics, and thermodynamic functions of conformers, as well as the structure and energy of transition states, were determined. IR spectrum of TPPN film contains vibrational bands belonging to different conformers. The assignment of bands was performed basing the distribution of normal vibration energy on internal coordinates. A synchronous electron diffraction/mass spectrometric experiment was performed to determine the structure of conformers in a saturated TPPN vapor. The elemental composition of the ions recorded in the mass spectrum indicates the thermal stability of TPPN at least up to T = 200 °C. The difference in the structure of tetrasubstituted metal phthalocyanines, which can be synthesized from different TPPN conformers, has been shown.

The conformational properties and structure of the conformers of 4-(4-tritylphenoxy)phthalonitrile (C 33 H 22 N 2 O), acting as a precursor for the synthesis of tritylphenoxy substituted phthalocyanines, were investigated by DFT method. The conformational analysis of the C 33 H 22 N 2 O molecule indicates the possibility of formation of conformers of substituted phthalocyanines with different orientations of 4-tritylphenoxy substituents, including those with a combination of cis-and trans-positions within one complex.

Based on the data of the gas electron diffraction/mass spectrometry (GED/MS) experiment, the composition of the vapor over rhenium tetrafluoride at T = 471 K was established, and it was found that species of the Re2F8 is present in the gas phase. The geometric structure of the Re2F8 molecule corresponding to D4h symmetry was found, and the following geometric parameters of the rh1 configuration were determined: rh1(Re-Re) = 2.264(5) Å, rh1(Re-F) = 1.846(4) Å, α(Re-Re-F) = 99.7(0.2)°, φ(F-Re-Re-F) = 2.4 (3.6)°. Calculations by the self-consistent field in full active space approximation showed that for Re2F8, the wave function of the 1A1g ground electronic state can be described by the single closed-shell determinant. For that reason, the DFT method was used for a structural study of Re2X8 molecules. The description of the nature of the Re-Re bond was performed in the framework of Atom in Molecules and Natural Bond Orbital analysis. The difference in the experimental values of r(Re-Re) in the free Re2F8 molecule and the [Re2F8]2− dianion in the crystal corresponds to the concept of a triple σ2π4 (ReIV-ReIV) bond and a quadruple σ2π4δ2 (ReIII-ReIII) bond, respectively, which are formed between rhenium atoms due to the interaction of d-atomic orbitals. The enthalpy of dissociation of the Re2F8 molecular form in two monomers ReF4 (ΔdissH°(298) = 109.9 kcal/mol) and the bond energies E(Re-Re) and E(Re-X) in the series Re2F8→Re2Cl8→Re2Br8 molecules were estimated. It is shown that the Re-Re bond energy weakly depends on the nature of the halogen, while the symmetry of the Re2Br8 (D4d) geometric configuration differs from the symmetry of the Re2F8 and Re2Cl8 (D4h) molecules.