The tetra(1,2,5-thiadiazolo)porphyrazine macrocycle coordinates Li⁺ forming an anionic lithate complex, which undergoes acid-catalyzed delithiation in aprotic solvents affording a dianion – a reactive precursor for the complexation reaction.

Geometric parameters, vibrational spectra, and the energies of isomerization of seven keto-enol isomeric forms of the H₂Salen molecule (N,N′-ethylene-bis(salicylidenimine)) are calculated using electron density functional theory (DFT/B3LYP) and correlation consistent valence triple-zeta Gaussian basis sets (cc-pvtz). The isomer with two enol groups (EE₁) and C ₂ symmetry configuration is most energetically favorable. Calculations of the keto-enol equilibrium show that at T ≥ 250 K the H₂Salen gas phase is a mixture of four conformers (rotamers of the main isomer EE₁). The contribution of other isomers does not exceed a few percent. The NBO analysis reveals that the system of π-conjugated bonds involves not only the atoms of the benzene moiety, but also the O, C, and N atoms nearest to the benzene ring. The energy stabilization of the isomer EE₁ is shown to be due to the presence of two strong intramolecular N...H hydrogen bonds. Intramolecular N...H and O...H hydrogen bonds are observed in all other isomers. The bathochromic shift of O-H and N-H vibrational frequencies, caused by the effect of hydrogen bonds, is 520–790 cm⁻¹.

Water-soluble sulfophenyl substituted P(v) corrolazines are effective photosensitizers in aqueous solutions. Fluorescence quenching accompanying the acid ionization of the central P(OH)₂ moiety can be used for the development of pH-sensors.

The molecular structures of potassium tetrakis(hexafluoroacetylacetonato)lanthanide(III) complexes [KLn(hfa)₄] (Ln=La, Gd, Lu; hfa=C₅HF₆O₂,) were studied by synchronous gas‐phase electron diffraction/mass spectrometry (GED/MS) supported by quantum‐chemical (DFT/PBE0) calculations. The compounds sublime congruently and the vapors contain a single molecular species: the heterobinuclear complex [KLn(hfa)₄]. All molecules are ofC₁symmetry with the lanthanide atom in the center of an LnO₈coordination polyhedron, while the potassium atom is coordinated by three ligands with formation of three K−O and three K−F bonds. One hfa ligand is not bonded to the potassium atom. Topological analysis of the electron‐density distributions confirmed the existence of ionic‐type K−O and K−F bonding. The structures of the free [KLn(hfa)₄] molecules are compared with those of the related compounds [KDy(hfa)₄] and [KEr(hfa)₄] in their crystalline state. The complex nature of the chemical bonding is discussed on the basis of electron‐density topology analyses.

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 D_4h symmetry was found, and the following geometric parameters of the r_h1 configuration were determined: r_h1(Re-Re) = 2.264(5) Å, r_h1(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 ¹A_1g 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 (Re^IV-Re^IV) bond and a quadruple σ²π⁴δ² (Re^III-Re^III) 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 (Δ_dissH°(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 (D_4d) geometric configuration differs from the symmetry of the Re₂F₈ and Re₂Cl₈ (D_4h) molecules.