Poled thin films of composite polymer materials based on PMMA doped with high thermally stable chromophores with the structure D-π-A1-π-A2 and D-π-A1A2 with a carbazole donor D, a quinoxalinone core, A1, either in a π-conjugated bridge or in a macroacceptor, were obtained. The effect of the chromophore structure on the values and long-term stability of the nonlinear optical coefficient, d33, of such thin films has been shown.

Dipole azinylmethylenemalononitrile-based chromophores with various fused azine (quinoline, quinoxaline and pyrido[2,3-b]pyrazine) moieties and bulky TBDPS-ethyl group in aniline donor fragment have been synthesized. Nonlinear optical (NLO) activity of poled PMMA films doped with such dyes has been investigated by second harmonic generation technique with in two approaches. Composite materials exhibit the growth of NLO performance at increasing dyes load from 25 wt% to 35 wt%. Polymer films doped with quinoxalin(on) ylmethylenemalononitrile-based chromophores demonstrate enhanced values of NLO coefficients, d33, up to 85 p.m./V.

Transition-metal-mediated white phosphorus activation provides access to diverse polyphosphorus complexes, yet their catalytic potential remains unexplored. Herein, we report the first catalytic application of such a complex,[Co(Ph2PNHP(Ph2)PPPPP(Ph2)NHPPh2)]BF4, in the hydrogen evolution reaction (HER). Mechanistic studies unveil a novel metal-assisted ligand-centred pathway, where the supramolecular dimerization and the subsequent CoIII-CoII reduction initiate the H2 release accompanied by the amino/aminido transformation in PNP fragment of the ligand. The main intermediates of the catalytic process were determined by synthetic and computational methods and characterized by spectroscopy and XRD analyses. The complex demonstrates high turnover frequency of 10,280 s(-1) at an 0.6 V overpotential with 99 % faradaic efficiency, comparable to the most efficient ligand-centred catalytic systems reported to date. The obtained results offer new insights into the design of molecular catalysts for sustainable hydrogen production.

Dimeric gold(I) complexes were synthesized by reaction of cyclic arsine ligands with chloro(tetrahydrothiophene)gold(I) in an equimolar ratio in methylene chloride. In the case of 10-(6-methylpyridin-2-yl)phenoxarsine, a monomeric structure with As-monodentate ligand was isolated. The complex was identified and characterized using a set of analytical methods (mass spectrometry, 1H NMR spectroscopy, elemental analysis, X-ray diffraction). Tolman angles were determined to assess the steric bulk of arsine ligands. DFT calculations were confirmed that the dimeric form is energetically more favorable compared to the monomeric structure.

Reactions of bis(3,5-dimethyl-1H-pyrazol-1-yl)-1-R-propan-1-ones (L1 and L2; R = phenyl and furanyl), potentially scorpionate-like ligands with MCl2 (M = Co(II) and Cu(II)) lead to formation of either [LMCl2] (L = L1, M = Co (1) and Cu (2), L = L2, M = Co (3)) or [L2CuCl]2[Cu2Cl6] (4) complexes, respectively. Within their structures, L are coordinated in N,N-bidentate mode while carbonyl units remain uninvolved in coordination. The structures were determined via X-ray diffractometry; electrochemical properties were examined for both native ligands and corresponding MCl2 complexes. According to UV–Vis data, the complexes are stable in presence of H2O2, thus being potentially applicable as oxidation catalysts.

The synthesis, structural and photophysical characterization of heteroleptic copper(I) complexes formulated as [Cu2I2L2Py2] (5-8), where Py = pyridine, with different 5,10-dihydro-10-(R)-phenarsazine ligands (R = phenyl, 4-metoxyphenyl, 3-metoxyphenyl and 4-bromophenyl) are reported. The structures of 5-8 were confirmed by 1H NMR and IR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. The luminescence properties were studied and rationalized by DFT calculations. In the solid state, under UV irradiation, all complexes exhibit a green emission, which was attributed to the halide/metal-to-ligand chargetransfer 3(X,M)LPyCT triplet state.

The reaction of [NiBr2(bpy)2] (bpy = 2,2 '-bipyridine) with 2,2 '-bibenzimidazole or 5,5 ',6,6 '-tetramethyl-2,2 ' bibenzimidazole (bbim) in the presence of AgBF4 and Et3N results in the formation of dinuclear nickel(II) complexes with bridging bbim ligands. The crystal structures of the obtained complexes [Ni2(mu-bbim)(bpy)4] [(BF4)2] have been determined. Variable-temperature EPR as well as magnetometry experiments indicate antiferromagnetic interactions between the nickel atoms in the complex molecule at low temperatures. Density functional theory (DFT) calculations confirm these findings. Cyclic voltammetry and in situ EPR spectroelectrochemistry demonstrated that these complexes can be electrochemically reduced resulting in the formation of Ni(I) and Ni(0) derivatives. This can be considered as a strategy for controlling the electronic state of these dinuclear nickel complexes, thus providing a way to design magnetic materials with switchable properties.

The electrochemical behavior of the N-heterocyclic carbene bisphenolate complex of nickel(ii) Ni(L)Py (L – 1,3-bis(3,5-di-tert-butyl-2-phenolato)-5,5-dimethyl-(4,6-dihydropyrimidin-2-ylidene)) was studied using cyclic voltammetry and EPR spectroelectrochemistry. According to the obtained experimental data supplemented by quantum chemical calculations, the electrochemical properties of this complex differ significantly from those of its benzimidazolylidene and imidazolylidene analogs. The oxidation of the Ni(L)Py complex is a ligand-centered process, and the phenoxyl radical group formed is susceptible to decoordination and interaction with the NHC-fragment of the complex to form benzoxazole, the crystal structure of which was determined by X-ray diffraction.

The reactions of 10-(aryl)phenoxarsines (L1 = 10-(4-tolyl)phenoxarsine, L2 is 10-(4-fluorophenyl)phenoxarsine, L3 is 10-(3-fluorophenyl)phenoxarsine, and L4 is 10-(2-methoxyphenyl)phenoxarsine) with Pt(COD)Br2 afford platinum(II) complexes [Pt(L1–4)2Br2] (I–IV). The complexes are characterized by elemental analysis, IR spectroscopy, mass spectrometry, and NMR (1Н, 13С, 195Pt) spectroscopy. The Pt(II) complexes in solutions exist as two isomers mutually exchanging at a rate intermediate in the NMR time scale. The molecular structures of complexes cis-II·chloroform, trans-II, and cis-IV·dichloromethane are determined by XRD (CIF files CCDC nos. 2368769 (cis-II·chloroform), 2368770 (trans-II), and 2368771 (cis-IV·chloroform)). The platinum(II) dibromide complexes can crystallize as both cis and trans isomers. The study of the photophysical properties of the platinum(II) complexes shows that the trans isomers are characterized by emission in the orange spectral range, whereas the cis isomers almost does not luminesce. 10-(Aryl)phenoxarsines and their platinum(II) complexes are tested to cytotoxicity against the M-HeLa and HuTu 80 human cancer cell lines and hepatocyte-like cells of the Сhang liver line.

Trends in changes in nonlinear optical (NLO) coefficients, d33, measured by the second harmonic generation technique for composite polymer materials doped with D-pi-A chromophores containing novel (quinoxalinylmethylene)malononitrile acceptor and various bulky groups in aniline donor (load 25/35 wt%), have been established. Structural modifications provided almost three-fold growth of material NLO activity at high chromophore load.

A series of new isatin hydrazones bearing phosphorus-containing moiety was synthesized through a simple, high-yield and easy work-up reaction of phosphine oxide (Phosenazide) or phosphinate (2-chloroethyl (4-(dimethylamino)phenyl)(2-hydrazinyl-2-oxoethyl)phosphinate, CAPAH) hydrazides with aryl-substituted isatins. The 31P NMR technique showed that, in most cases, out of 12 examples in solution, the ratio of the two spatial isomers varied from 1:1 to 1:3. Quantum chemical calculations confirmed the predominance of Z,syn form both in the gas phase and in solution. According to X-ray analysis data in crystals, they exist only in Z,syn form too. Most of the phosphine oxide derivatives and 5-methoxy- and 5-bromoaryl phosphinate analogs exhibit anti-aggregant activity at the level of acetylsalicylic acid but inhibit platelet activation processes more effectively. The 5-chloro type phosphinate derivative exhibits anti-aggregant properties more effectively than acetylsalicylic acid under the conditions of the tissue factor (TF)-activated thromboelastography (TEG) model, the ex vivo thrombosis model. Thus, all the obtained results can become the basis for future pharmaceutical developments to create effective anti-aggregation drugs with broad antithrombotic potential.

A series of alkyl[2-(5-chloro-2-hydroxyphenyl)hex-1-en-1-yl]diphenylphosphonium salts were synthesized based on the predicted lipophilicity (logP). The synthesized salts exhibited high antimicrobial activity against gram-positive bacterial and fungal strains and high activity against the antibiotic-resistant Staphylococcus aureus (MRSA) strains. The most active compounds showed low cytotoxicity against human erythrocytes and liver cells and exhibited high selectivity indices.

D-π-A chromophores based on novel macroacceptors − fused azinylmethylenemalononitriles (fused azine = pyrido[2,3-b]pyrazine, quinoline, quinoxaline and quinoxalin-2-one) − have been synthesized and their linear and nonlinear optical properties in gas, solution and in poled PMMA-based films have been investigated by DFT, UV-vis and second harmonic generation technique. The transition from chromophores with an azine acceptor to ones with azinylmethylenemalononitrile acceptors leads to a 10-fold increase in calculated μβ values. Poled polymer films doped with studied chromophores at 25wt% load exhibit quadratic nonlinear optical activity with d33 values up to 42 pm/V.

The electrochemical properties of [Co(Ph2PCH2P(Ph)2PPPPP(Ph)2CH2PPh2)]BF4 complex have been studied by the method of cyclic voltammetry. The electrochemical methylation of this complex have been cunducted in the presence of iodomethane which has led to the formation of phosphonium salt—ethylene bis(methyldiphenylphosphonium) diiodide as final product. It was found, that this reaction proceeds with the breakage of the P–P bonds in polyphosphorus ligand and with the formation of new P–C bonds.

The electrochemical properties of [Co(Ph2PCH2P(Ph)2PPPPP(Ph)2CH2PPh2)]BF4 complex have been studied by the method of cyclic voltammetry. The electrochemical methylation of this complex have been cunducted in the presence of iodomethane which has led to the formation of phosphonium salt—methylene bis(methyldiphenylphosphonium) diiodide as final product. It was found, that this reaction proceeds with the breakage of the P–P bonds in polyphosphorus ligand and with the formation of new P–C bonds.

The luminescence properties of a synthesized series of Cu 4 I 4 clusters with a stair-step, cubane, and octahedral geometries supported by novel As,N-ligands, were reported and rationalized.

The electrochemical properties of bis[2-(di-i-propylphosphino)-4-methylphenyl]amido complexes [(PNP)MCl] of Ni, Pd and Pt have been investigated by experimental electrochemical methods involving cyclic voltammetry (CV), in situ UV-vis- and EPR-spectroelectrochemistry, and density functional theory (DFT) calculations. A combination of spectroscopic and theoretical techniques suggests the formation of aminyl-radical complexes as a result of the electrooxidation process. The photophysical behavior of the electrochemically generated species was studied by in situ EPR measurements with photoexcitation, which revealed the formation of free aminyl radical through the cleavage of the ligand-metal bonds. Finally, the electrochemical generation and spectroelectrochemical studies of the hydride derivative [(PNP)PdH] allow the determination of the aminyl-radical hydride complex [(PNP)PdH][BF4], which has been generated with 33 % yield.

Silver(I) nitrate complexes [(L)3Ag(NO3)] have been synthesized by the reactions of AgNO3 with 10-(aryl)phenoxarsines (L) in ethanol. The structures of complexes are elucidated by spectral methods and X-ray diffraction. All complexes demonstrate moderate to enhanced antimicrobial activity against both Gram-positive and Gram-negative bacteria, fungi as well as cytotoxicity against human cervix epithelioid carcinoma (M-HeLa) and human duodenal adenocarcinoma (HuTu 80) cell lines.

Бас редактор: ЖҰРЫНОВ Мұрат Жұрынұлы, химия ғылымдарының докторы, профессор, ҚР ҰҒА академигі, Қазақстан Республикасы Ұлттық ғылым академиясының президенті, АҚ «Д.В.Сокольский атындағы отын, катализ және электрохимия институтының» бас директоры (

1D coordination silver(I) polymer [L 2 AgONO 2 ] n has been obtained via the reaction of 10-(4-ethoxyphenyl)phenoxarsine with silver(I) nitrate (metal : ligand molar ratio 1 : 2) in ethanol. The complex has been identified and characterized by a set of physicochemical methods of analysis (mass spectrometry, 1 H NMR spectroscopy, elemental analysis, and X-ray diffraction analysis). The ligand and its Ag(I) complex have been evaluated for cytotoxicity against the cancer cell lines M-HeLa and HuTu 80 and the normal cell line Chang liver; antimicrobial activity of the complex against a series of Gram-positive and Gram-negative bacteria has been investigated.