Mononuclear nickel complexes [NiL1(NCS)2]·2DMSO (I), [NiL1(NCS)2]·DMF (II), and [NiL2(NCS)2]·0.5CH3OH·1.5H2O (III) with the distorted octahedral coordination node, where L1 and L2 are the tetradentate ligand systems derived from the products of the condensation of diacetyl with 2-hydrazinoquinoline and 2-hydrazino-4,6-dimethylpyrimidine, respectively, are synthesized. The structures of the compounds are determined by IR spectroscopy and XRD (CIF files ССDС nos. 2219793 (I), 2142035 (II), and 2219794 (III)). The quantum chemical modeling of the axial parameter of magnetic anisotropy in the zero field (D) is performed for the synthesized compounds in the framework of the SA-CASSCF+NEVPT2 method. The complexes are shown to be characterized by three-axis magnetic anisotropy close to the light magnetization plane with positive D. The axial parameter of magnetic anisotropy (Dexp = 8.79 cm−1) determined by the approximation of the magnetometry data on complex [NiL2(NCS)2]·0.5CH3OH·1.5H2O is consistent with the calculated value (Dcalc = 11.5 cm−1).

Quantum-chemical calculations of the geometric and electronic structures of Fe2O7 and Fe2O9 clusters, as well as the interaction of Fe2O7 with H2 and O2 molecules and Fe2O9 with an H2 molecule in the gas phase, have been performed by the density functional theory method in the generalized gradient approximation using a triple-zeta basis set. Differences in the heats of the reactions of the clusters with H2 and O2 molecules have been found. It has been demonstrated that in the case of the reaction of Fe2O7 with an H2 molecule, the total spins of the initial reactants and the final products do not coincide, that is, spin relaxation occurs during the reaction.

The crystal and molecular structure of a polynuclear pivalate complex obtained by the interaction of ZrCl4 with pivalic acid is determined by X-ray diffraction analysis. The compound C71H124O28Zr4 crystallizes in a monoclinic crystal system. The crystal structure is refined in the nonstandard space group I2. The asymmetric part of the structure includes three Zr atoms, six pivalate ligands, and a bridging µ3-O oxygen atom, as well as disordered crystallization molecules of pivalic acid with an occupancy of 50

During the evaporation of magnesium and calcium in partially dissociated H2, a glow with λ = 4571.15 and 6572.78 Å is detected, corresponding to the transitions ^3P_1^0 → 1S0 in excited Mg* and Ca* atoms. It is assumed that this phenomenon is associated with the chemiluminescence of these atoms when they interact with H atoms.

Spiropyran salts containing a cationic vinyl-3H-indolium moiety are characterized by NIR absorption and fluorescence of their merocyanine forms. This feature makes them promising fluorescent probes and markers for bioimaging. The article focuses on the synthesis and study of the spectral, kinetic and toxic characteristics of such compounds with respect to various substituents in different moieties and the type of anion. A detailed analysis of the acquired data made it possible to draw some important conclusions regarding the influence of structural factors, which will be very useful for the further rational design of such derivatives. In particular, it was shown that the counterion has minimal effect on the spectral and kinetic characteristics of the dyes but dramatically affects the toxicity of the compounds. Following selection of the most appropriate compounds, bioimaging experiments were carried out to visualize planktonic bacteria and bacterial biofilms of E. coli and A. calcoaceticus. The ability to visualize biofilms is critical for the diagnosis of chronic diseases. By the results of molecular docking a theoretical interaction pattern between spiropyran molecules and DNA was proposed.

Recently the need for smart materials has been extremely growing, and the development of materials with appropriate characteristics has become one of the main challenges. Heptamethine cyanine dyes are widely used in theranostics and photovoltaics due to their remarkable optical properties. However, they are characterized by "rigid" non-changable properties. The main aim of the current study is to unveil correlation between structure and optical properties in the range of vinyl-3H-indolium substituted spiropyrans, which can be considered as the closest analogs of heptamethine cyanines with the photocontrolable optical and fluorescent properties. The effects of substitution in indoline and 2H-chromene cycles, as well as anion change are under the study. To achieve this goal, a series of spiropyran iodides and perchlorates with methyl, methoxy substituents or fluorine atom in position 6 ', as well as a conjugated vinyl-3H-indolium fragment in position 8 ', were synthesized. The structure of the compounds was carefully studied using SC XRD, NMR, IR and mass spectroscopy. Then, studies on absorption and photoluminescence characteristics, as well as photochromic behavior were carried out. A series of spiropyran iodides and perchlorates with methyl, methoxy and fluorine substituents in position 6 ', as well as a conjugated vinyl-3H-indolium fragment in position 8 ', were synthesized. The structure of the compounds was carefully studied using NMR, IR and mass spectroscopy, as well as SC XRD. Studies on absorption and photoluminescence characteristics, as well as photochromic behavior were carried out. image

Three new binuclear iron tetranitrosyl complexes with m- and p-methoxybenzenethiolate and naphthalene-2-thiolate ligands were synthesized. The crystals of the new complexes were characterized by X-ray diffraction, IR spectroscopy, Mössbauer spectroscopy, and elemental analysis. The synthesized complexes were evaluated for nitric oxide-donor properties, cytotoxicity against cancer and normal cell lines, and antibacterial activity. The complexes and the corresponding ligands have different toxicity in cells of different origin; in some cases, the ligands exhibit higher cytotoxicity compared to the complexes. The complexes exhibited antibacterial activity comparable to that of the antibiotic kanamycin, while the ligands did not possess antibacterial activity. The complex with the m-methoxybenzenethiolate ligand inhibits the biofilm formation of the bacteria Micrococcus luteus with an efficiency comparable to that of ampicillin and kanamycin.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Quantum-chemical calculations of the geometric and electronic structures of compounds formed by the interaction of Fe 2 O 2 and Fe 2 O 4 clusters with diatomic H 2 and O 2 molecules in the gas phase have been performed by the density functional theory method in the generalized gradient approximation using the triple-zeta basis set. The trends in changes in the binding energy of H 2 and O 2 molecules with Fe 2 O 2 and Fe 2 O 4 clusters depending on the number of oxygen atoms have been found. It has been demonstrated that in two of the four reactions considered, the total spins of the initial reagents and final products do not coincide, that is, spin relaxation occurs. It has been concluded that nanoparticles based on Fe 2 O 4 clusters can be used as sensors for detecting H 2 and O 2 molecules.

The structures of 3,5-di-(tert-butyl)-2-hydroxyazobenzene (L) in the free state and in complexes with Ni2+ (I) and Pd2+ (II) cations are studied by X-ray diffraction (XRD). The same space group R 3̅ с with close unit cell parameters, the same crystal structure motif, and unusual conformations of the cupola-shaped coordination polyhedra of complexes I and II are revealed by XRD for ligand L. In complexes I and II based on this compound as the ligand, the coordinating atoms form trans-planar coordination nodes.

A novel neutral tetranitrosyl iron complex {[Fe(H2O)4]2+[FeR2(NO)2]22-}·4H2O (1) with R = 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiolyls (C7H5N4S), which is a supramolecular ensemble, has been synthesized and studied. As follows from X-ray diffraction analysis, this is an octahedral Fe2+complex (Lewis acid) with two monoanionic dinitrosyl groups [FeR2(NO)2]- (Lewis base) and 4 water molecules as the ligands. As follows from Mössbauer spectra, the coordinating Fe2+ ion is in a low-spin state S = 0, and the dinitrosyl Fe+ ion is in a low-spin state S = 1/2. According to the data of EPR spectroscopy, mass-spectrometry and amperometry, complex 1 in solution forms dinitrosyl particles of [Fe(C7H6N4S-H)2(NO)2]- composition, which are responsible for NO generation. In addition, complex 1 was shown to be a 5-6 times more efficient phosphodiesterase (PDE) inhibitor at 5 × 10-5 M and 10-4 M concentrations than its thioligand. Probable binding sites of the [FeR2(NO)2]- ligand for the bovine PDE1B model have been determined by molecular docking and quantum-chemical calculations.

Впервые синтезированы 7-цианометил-7 Н -дифуразано[3,4- b :3',4'- f ]фуроксано[3",4"- d ]азепин ( Az(O)CH 2 CN ) и 7-цианометил-7 Н -трифуразано[3,4- b :3',4'- d :3",4"- f ]азепин ( AzCH 2 CN ) как потенциальные диспергаторы твердых топлив для газогенераторных двигателей; определена их молекулярная структура, энтальпии сгорания и образования; оценена относительная дальность полета летательного аппарата при использовании Az(O)CH 2 CN и AzCH 2 CN в качестве диспергаторов топлива.

Effect of the anion nature on crystal structure of Zn-complexes of spironaphthopyran and their chromogenic properties in solution were studied. Complexes with zinc chloride and zinc picrate exhibited tertahedral and octahedral coordination environment of the metal ion respectively. The structure of the complex with zinc picrate demonstrates a rare example of the co-crystallization of two types of complexes differing in the number of coordinated picrate anions. The composition, stability, and absorption properties of zinc complexes in acetone essentially depend on the counter anion nature. When the coordinating ability of the counter ion increases in the range BF4- , ClO4- , NO3-, Pic-, I-, Cl-, CH3COO-, (CH3)3CCOO- the complex stability is reduced from logK = 8.7 to 2.96. This is accompanied by the chromogenic effect which is related to the decrease in the spectral shift of the long-wavelength absorption band of the complex relative to the merocyanine ligand from 846 up to 168 cm-1. The complex photo-initiated processes include fluorescence and thermally reversible dissociation. Fluorescence is characterized by band maxima in the 622-637 nm region and normal Stokes shifts of 1087-1454 cm-1 with an efficiency being weakly dependent on the anion nature. In contrast, the negative photochromism of the complexes demonstrates a significant dependence of the photo-bleaching efficiency on the anion nature in the range 0.012-0.17. The presence of a chromogenic photochromic effect along with fluorescence makes it possible to consider the complex as fluorescent switch.

New indoline spiropyrans containing chlorine and bromine atoms in position 5 of the indoline moiety of the molecule as a substituent were synthesized and studied. The structures of the synthesized compounds were confirmed by NMR and IR spectroscopy. The molecular structure of the chlorine-substituted derivative was determined by X-ray diffraction analysis, and intermolecular interactions in the crystal were studied using the CrystalExplorer21.5 software package. The spectral kinetic studies revealed photochromic properties of novel spiropyrans in an acetonitrile solution. The photoelectrochemical characteristics of dye-sensitized solar cells (DSSC) made from the synthesized compounds before and after UV irradiation were studied in comparison.

Based on the previous experimental and theoretical studies of the unusual dome-shaped structures of Pd II and NiII 3,5-di(tert-butyl)-2-oxyazobenzene complexes, gas-phase quantum chemical calculations were performed for related model CuII, CoII, FeII, MnII, CrII, and ZnII complexes. The calculations were carried out with full geometry optimization at the TPSSh/def2tzvp(Cu,Co,Fe,Mn,Cr,Zn)/6-311G*(C,N,O,H) level of theory. All compounds were calculated in the low-spin and high-spin states — singlet and triplet for FeII, CrII, ZnII and doublet and quartet for CuII, MnII, CoII. Metal complexes with a closed shell (Zn), a half-filled shell (Cr), and a half-filled d-subshell (Mn) have a tetrahedral structure in the gas-phase ground energy state, whereas CuII-, CoII-, and FeII-based complexes have an unusual dome-shaped structure.

The geometry and electronic structure of the Fe 2 O, Fe 2 O 3 , and Fe 2 O 5 clusters and the products of their interaction with H 2 and O 2 in the gas phase have been calculated by the density functional theory method in the generalized gradient approximation using the triple-ζ basis set. Trends in bond energies of H 2 and O 2 in the products of the Fe 2 O 2 n + 1 + O 2 and Fe 2 O 2 n + 1 + H 2 ( n = 0–2) reactions have been found. According to computational results, the initial total spin magnetic moment in the Fe 2 O 3 + H 2 → Fe 2 O 3 H 2 reaction is not conserved, and the antiferromagnetic states of the reactants are transformed into the ferrimagnetic state of the reaction product. Conversely, the addition of H 2 to Fe 2 O 5 (triplet) leads to the singlet ground state of Fe 2 O 5 H 2 . The calculated activation barriers for the Fe 2 O 2 n + 1 + H 2 and Fe 2 O 2 n + 1 + O 2 reactions are relatively low and do not exceed 33 kcal/mol for all values of 2 n + 1 = 1, 3, and 5.

This work aims at the synthesis and investigation of a new series of antibacterial agents, viz dimers of dinitrosyl iron complexes (DNICs) of [Fe2(SR)2(NO)4] composition, where R is 5-(2-nitrophenyl)-4-H-1,2,4-triazole-3-thiolyl (I), 5-(3-nitrophenyl)-4-H-1,2,4-triazole-3-thiolyl (II), 5-(4-nitrophenyl)-4-H-1,2,4-triazole-3-thiolyl (III), that are nitric oxide (NO) donors, easily obtained by replacement of thiosulfate ligands in [Fe(S2O3)2(NO)2]2- anion. Based on investigation of the structures of I and its isostructural analogs II and III (X-ray analysis, quantum-chemical calculations in the frame of DFT using NBO and QTAIM methods), data have been obtained on molecular interactions stabilizing DNIC dimer of µ–N–C–S structural type functionalized by 5-(2-nitrophenyl)-4-H-1,2,4-triazole-3-thiolyl. NBO calculations provided the assessment of bond energy for the Fe-S and Fe-N bonds incorporated in the µ–N–C–S bridge. From QTAIM analysis, detailed information on the nature and covalence of the forming bonds has been obtained. Assessment of antibacterial activity of I-III with respect to gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria has been performed.

Quantum chemical calculations of the molecular and electronic structure of the complexes [(L)2M13+(L)M22+(L)2]5− (M13+ is the Mo ion in the oxidation state +3; M22+ is the 3d and 4d transition-metal (Fe, Ru, Rh, Pd) ion in the oxidation state +2; and L is the dithiooxamide ligand) were carried out to search for pairs of metals corresponding to the maximum value of the exchange coupling constant J. Molecular structure calculations of the complexes were performed in the B3LYP/LANL2DZ approximation while the J constants were obtained from B3LYP/TZV calculations. It was shown that replacement of 3d transition-metal ions in the oxidation state +2 by 4d transition-metal ions in the oxidation state +2 leads to higher J values. It was established that the J values change in parallel with the difference between the total spin density on the M13+ and M22+ metal ions in the complexes and in the isolated M13+ and M22+ ions.

Reaction of 1-phthalazinylhydrazone of o-diphenylphosphinobenzaldehyde (HL) with Fe(II) and Co(II) perchlorates has led to complexes of different composition and structure: [Fe(HL)2](ClO4)2 · H2O (1) and [CoL2](ClO4) · H2O (2) in spite of the use of salts with the same anion. Со2+ ion undergoes oxidation to Co3+ upon complexation. The structure of the complexes has been established by NMR spectroscopy in solution and by X-ray diffraction in crystal. X-ray diffraction has shown that complexing metal ions have octahedral structure. Compound 2 forms two independent molecules in crystal.

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