M. A. Samsonov

Cyclometallated Iridium(III) Complex with the Norbornene Substituted Pyrazolonate Ligand and Related Copolymers: Syntheses, Structures, and Photophysical Properties

New cyclometallated iridium(III) complex (NBEpz)Ir(Ppy)2 · 2CH2Cl2 (I) (NBEpzH is 1-phenyl-3-methyl-4-(5-bicyclo[2.2.1]hept-5-en-2-yl)-5-pyrazolone, PpyH is 2-phenylpyridine) is synthesized and structurally characterized. Compound I undergoes metathesis polymerization and forms new iridium-containing copolymers. The photophysical properties of complex I and related copolymers are studied.

Reversible binding of molecular oxygen to catecholate and o-amidophenolate complexes of SbV: energy approach

The theoretical study of the reactivity of catecholate and o-amidophenolate complexes of SbV in the reversible binding of molecular oxygen was performed. The evaluation of the strength of intramolecular interactions in pre-reaction complexes provides the assessment of the strength of oxygen binding in the coordination sphere of Sb. The initial complexes, their transition states, and final spiroendoperoxide complexes were modeled. The calculated activation energies of the reaction and ionization can serve as the energy criteria providing the explanation and prediction of interactions of these complexes with molecular oxygen.

Experimental and theoretical investigation of topological and energy characteristics of electron density in crystals of SbVo-amidophenolate complexes

Experimental and theoretical investigations of electron density in the complexes [4,6-ditert-butyl-N-(2,6-diisopropylphenyl)-1,2-amidophenolato]tricyclohexylantimony(V) (1) and [4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-1,2-amidophenolato]tri-4-fluorophenylantimony(V) (2) were performed based on high-resolution X-ray diffraction data and density functional theory calculations (B3LYP/DGDZVP). The nature of chemical bonding, the energy of intraand intermolecular interactions in the crystals, and the atomic charge distribution were studied.

ate complexes of lanthanides with aryloxide ligands: Synthesis, structures, and luminescence properties

Abstract(2-Benzox(thi)azol-2-yl)phenolate and -naphtholate ate complexes of Sc, Y, La, Sm, Tb, and Yb are synthesized. The structure of (benzoxazolyl)phenolate complexes of La, Sm, and Yb are determined by X-ray diffraction analysis. All synthesized compounds manifest ligand-centered photo- and electroluminescence in a range of 510–540 nm. In addition, the spectra of the samarium and terbium complexes exhibit narrow bands of f-f transitions characteristic of Sm3+ and Tb3+ ions.

Complexes of gallium(III), antimony(III), titanium(IV), and cobalt(II) with acenaphthenequinonimine

Reactions of (2,6-diisopropylphenylimino)acenaphthenone (dpp-mian) with gallium(III), antimony(III), titanium(IV), and cobalt(II) chlorides in toluene lead to the formation of compounds of the formulas [(dpp-mian)2GaCl2][GaCl4], (dpp-mian)SbCl3, (dpp-mian)TiCl4, and [(dpp-mian)CoCl2]2[CoCl2(EtOH)4], respectively. The complexes were characterized by IR and NMR spectra, their structure was established by X-ray crystallography.

Electron density distribution in crystals of the antimony(V) spiroendoperoxide complexes

The experimental and theoretical electron densities in complexes [6-(2,6-di-iso-propylphenyl)imino-2,4-di-tert-butylcyclohexa-2,4-diene-1-peroxo-1-olato-N,O,O′]tris(p-chlorophenyl)antimony(V), (p-Cl–C6H4)3Sb(2,6-iso-Pr–Ph–AP) · O2 (I), and [6-(2,6-dimethylphenyl)imino-2,4-di-tert-butylcyclohexa-2,4-diene-1-peroxo-1-olato-N,O,O′]tris(p-chlorophenyl)antimony(V), (p-Cl–C6H4)3Sb(2,6-Me–Ph–AP) · O2 (II), where AP is 4,6-di-tert-butyl-N-o-iminobenzoquinone dianion, are studied on the basis of high-resolution X-ray diffraction data and theoretical calculations using the density functional theory (B3LYP/DGDZVP). The nature of chemical bonds and the charge distribution on atoms are studied, and the energy of molecular oxygen addition to the Sb(V) o-aminophenolate complexes is estimated. The structures are deposited with the Cambridge Crystallographic Data Centre (CIF files CCDC nos. 1560600 (spherical refinement) and 1560601 (multipole refinement) for complex I; 1560602 (spherical) and 1560603 (multipole) for complex II).

Aluminum hydrides with radical-anionic and dianionic acenaphthene-1,2-diimine ligands

The reaction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with LiAlH4 affords two products regardless of the solvent used (tetrahydrofuran or diethyl ether). These products were isolated as green and colorless crystals. Green crystals of the complex [(dpp-bian)Al(H)2Li(THF)3] (1) were obtained from tetrahydrofuran; colorless crystals of the complex [{dpp-bian(H2)}Al(H)2Li(Et2O)2] (2), from diethyl ether. The reactions of compound 1 with 2,6-di-tert-butyl-4-methylphenol and benzophenone gave monohydrides [(dpp-bian)Al(H)(OC6H2-2,6-Bu2t-4-Me)][Li(THF)4] (3) and [(dpp-bian)Al(H)(OCHPh2)- Li(THF)2] (4), respectively. The diamagnetic aluminum hydride [(dpp-bian)AlH(THF)] (5) was synthesized by the reaction of dichloroalane HAlCl2 (in situ) with the disodium salt of dpp-bian in THF; the paramagnetic hydride [(dpp-bian)AlH(Cl)] (6) containing the dpp-bian radical anion was synthesized by the reaction of the monosodium salt (dpp-bian)Na with monochloroalane H2AlCl (in situ) in diethyl ether. The reaction of compound 6 with tert-butyllithium gives the complex [(dpp-bian)AlBut(Et2O)] (7). Diamagnetic derivatives 1—5 and 7 were characterized by 1Н NMR spectroscopy; paramagnetic compound 6, by ESR spectroscopy. The molecular structures of compounds 1—7 were determined by single-crystal X-ray diffraction.

Reactions of alkyl compounds of zinc, cadmium, and gallium with dysprosium, neodymium, and thulium diiodides

The ethyl complexes of dysprosium DyI2Et(DME)2 and DyIEt2(DME)2 were synthesized by the reaction of DyI2 with ZnEt2 in dimethoxyethane. The complexes were isolated as pale yellow crystals. According to the X-ray diffraction data, these compounds contain, in addition to DyI2Et(DME)2 and DyIEt2(DME)2, triiodide DyI3(DME)2 (1). The reactions of CdMe2 with NdI2, DyI2, and TmI2 proceed in a similar way and afford methyl iodide complexes of lanthanides. The reaction of GaEt3 with DyI2 gave the ionic complex of trivalent dysprosium [GaEt4]−[DyI2(THF)5]+ (2).

Monophthalocyanine complexes of samarium and terbium with axial ligands: synthesis, structure and optoelectronic properties

Abstract The monophthalocyanine complexes of samarium and terbium containing axial 2-mercaptobenzothiazole (PcSm(MBT) (1)), 2-(2-benzoxazol-2-yl) phenolate (PcTb(OON) (2)) or 2-(2-benzothiazol-2-yl)phenolate (PcTb(SON) (3)) ligands were synthesized and identified by elemental, LDI-TOF and X-ray (for 1) analysis. Photoluminescence (PL) and electroluminescence (EL) spectra of the compounds contained only emission bands of phthalocyanine and axial ligands but did not contain the bands of f-f transitions. It was found that among the complexes 1, 2, 3 the latter had highest photoconductivity (~10−7 S/cm) and photovoltaic properties. An organic photovoltaic device (OPV) of configuration of ITO/3/C60/Alq3/Al revealed open-circuit voltage (VOC) of 0.24 V and short current density (ISC) of 0.3 μA/cm2 under illumination by a xenon lamp at 17 mW/cm2.

Potassium carbazolyl complexes with coordinating solvents: Syntheses and crystal structures

The reaction of carbazole with KOH in dimethylformamide (DMF) at 75°C for 1.5 h affords CarbK(DMF) (CarbH is carbazole) in 90% yield. The crystallization of the compound from DME, CH3CN, and CD3CN gives complexes CarbK(DME)2, CarbK(DMF)(CH3CN), and CarbK(DMF)(CD3CN), respectively, whose structures are determined by X-ray diffraction analyses. The dissolution of CarbK(DMF)(CH3CN) in CD3CN results in the deuterium exchange in the bound solvent to form complex CarbK(DMF)0.5(CD2HCN)1.5, whose structure is also established by X-ray diffraction analysis.