Synthesis, structural characterization, and initial electroluminescent properties of bis-cycloiridiated complexes of 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine

A series of bis-cyclometalated Ir(III) complexes (8-10, 12, 15, 17, 19, 21, 23, 25, 28, 29 and 33) bearing two chromophoric N^∧C cyclometalated ligands derived from 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1) and a third nonchromophoric ligand has been synthesized. A palladium-catalyzed cross-coupling reaction between 2-chloro-4-methylpyridine (2) and 3,5-bis(trifluoromethyl)phenylboronic acid (3) was used to prepare 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1). Cyclometalation of (1) by IrCl₃ was carried out in (MeO)₃PO, with the formation of chloro-bridged dimer [N^∧C]₂Ir(μ-Cl)₂Ir[C^∧N]₂ (8). Reaction of (8) with lithium 2,4-pentanedionate, lithium 2,2,6,6-tetramethyl-heptane-3,5-dionate (13), dipivaloyltrimethylsilylphosphine (14), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octadione (16), 1,1,1,3,3,3-hexafluoro-2-pyridin-2-yl-propan-2-ol (18), 1,1,1,3,3,3-hexafluoro-2-pyrazol-1-ylmethyl-propan-2-ol (20), 2-diphenylphosphanylethanol (22), and 1-diphenylphosphanylpropan-2-ol (24), afforded octahedral iridium complexes 9, 12, 15, 17, 19, 21, 23 and 25, respectively. Complex 10, which contains three different ligands (L₁ = N^∧C of 1; L₂ = N^∧C of 4,4′-dimethyl-[2,2′]bipyridinyl 4; L₃ = O^∧O of 2,4-pentanedione), and complex 11, which contains no cyclometalated ligands (L₁ = 4; L₂ = L₃ = Cl; L₄ = O^∧O of 2,4-pentanedione) were also isolated as minor products in a one-pot reaction between a 94:5 mixture of 1 and 4, IrCl₃ and lithium 2,4-pentanedionate. Reaction of 8 with diphenylphosphanylmethanol (27) in 1,2-dichloroethane unexpectedly led to complexes 28 and 29. The reactions of 8 with benzoylformic acid resulted in the formation of hydroxyl-bridged dimer [N^∧C]₂Ir(μ-OH)₂Ir[C^∧N]₂ (33). According to X-ray analyses, Ir-to-Ir distances in the crystal cell increase from 6.86 Å for 10 to 13.31 Å for 33. The angle theta, which represents the twisting of two cyclometalated C-Ir-N planes relative to each other, varies from 97.5° for 21 to 90.76 for complex 28. OLED devices were fabricated from several Ir complexes and preliminary results are discussed.     

Loss of electrons by fast H− ions in gases

The characteristic angles and cross sections for a (\mathop 1^- 0) + (\mathop 1^- 1)(\mathop 1\limits^ - 0) + (\mathop 1\limits^ - 1) reaction in which H⁻ atoms with an energy of 0.1–10 000 MeV lose electrons when scattered on C, N, or O atoms were calculated for the relativistic case of the Bethe scattering theory. The cross sections for N₂, O₂, and CO₂ molecular targets were obtained using the additivity rule. The results presented are compared with known experimental and theoretical data.     

Trends in the kinetic and magnetic properties of Pb0.8Sn0.2Te single crystals of high structural perfection

In the temperature interval 4.2–300K and magnetic fields up to 4 T, we have investigated the electrical, thermal-electrical, thermal-magnetic, and magnetic properties of single crystals of the solid solution Pb_0.8Sn_0.2Te. It is shown that an enhancement of its level of structural perfection leads to the appearance of a second structural phase transition (SPT), and also to an increase in the temperature of the first structural phase transition. Fiz. Tverd. Tela (St. Petersburg) 41, 1750–1752 (October 1999)     

Photoaddition of N-substituted piperazines to C60: an efficient approach to the synthesis of water-soluble fullerene derivatives

An oxidative radical photoaddition of mono N-substituted piperazines to [60]fullerene was systematically investigated. Reactions of C60 with piperazines bearing bulky electron-withdrawing groups (2-pyridyl, 2-pyrimidinyl) were found to be the most selective and yielded C60(amine)4O as major products along with small amounts of C60(amine)2. In contrast, interactions of fullerene with N-methylpiperazine and N-(tert-butoxycarbonyl)piperazine were found to have low selectivity due to different side reactions. Tetraaminofullerene derivative C60(N-(2-pyridyl)piperazine)4O was found to react readily with organic and inorganic acids to yield highly water-soluble salts (solubility approximately 150 mg mL(-1)). In contrast, C60(N-(2-pyrimidinyl)piperazine)4O undergoes hydrolysis under the same conditions and results in a complex mixture of compounds with an average composition of C60(N-(2-pyrimidinyl)piperazine)2(OH)2O. Radical photoaddition of N-(2-pyridyl)piperazine to fullerene derivatives can be used as a facile route for their transformation into water-soluble compounds. Two model fullerene cycloadducts (a methanofullerene and a pyrrolidinofullerene) were easily converted into mixtures of regioisomers of A=C60(N-(2-pyridyl)piperazine)4O (A=cyclic addend) that give highly water-soluble salts under acid treatment.     

Energy version of the kinetic equations of isothermal creep and long-term strength

Energy-type kinetic equations of inelastic rheological deformation are proposed in which the elastic, plastic, and creep strains are the additive components of the total strain, and the damage parameter is taken into account. A model of viscoelastic material with a creep kernel of exponential type is considered. The Lyapunov stability of solutions under constant stress is studied. The stability range of the solutions of the differential equations of the mathematical model corresponding to asymptotically bounded creep is established. It is shown that the instability range of the solutions corresponds to the onset of the third stage of creep. The relationship is determined between the Lyapunov stability of the solutions and the stability of the computational algorithm for the numerical solution of the system of equations. The proposed model is experimentally verified. It is shown that the calculated and experimental data are in good agreement.     

Heat equation with a general stochastic measure on nested fractals

A stochastic heat equation on an unbounded nested fractal driven by a general stochastic measure is investigated. Existence, uniqueness and continuity of the mild solution are proved provided that the spectral dimension of the fractal is less than 4/3.     

Active media based on SiO2 matrices with incorporated molecules of rhodamine dyes

SiO₂ matrices with incorporated molecules of Rhodamine 6G and Rhodamine 800 laser dyes were synthesized by the sol?Cgel method. The spectral properties of the matrices were studied. It was found that the incorporation of Rhodamine 6G molecules into the xerogel network decreased their association. The influence of the molar ratio of water and formamide on the transparency of the samples was studied. Laser emission of SiO₂ matrices activated with Rhodamine 800 was obtained in the near infrared spectral range. The values of laser spectrum halfwidth of SiO₂ matrices with Rhodamine 6G and Rhodamine 800 are 2?C6?nm. A well-defined structure of the laser emission spectra of the matrices at microsecond pumping duration testifies to their relatively high optical quality.     

On the Existence of the Trimer of Gallium Trichloride in the Gaseous Phase

The dependence of the gallium trichloride saturated and unsaturated vapor pressures on temperature was studied by the static method using a quartz membrane zero‐manometer and taking into account the volume of its working chamber and substance mass. Conclusions about the presence of a distinguishable amount of trimeric molecules along with dimeric and momomeric molecules in the vapor were drawn on the basis of the obtained data. The following rough thermodynamic characteristics of a gaseous trimer of gallium trichloride were calculated: Δ_fH° (Ga₃Cl₉, gas, 298 K) = –1466 kJ · mol^–1. S°(Ga₃Cl₉, gas, 298 K) = 654 J · mol^–1 · K^–1. These data were used to elucidate the composition of the gaseous phase at a total pressure of 1 atm in the temperature range of 400–750 K. The suggested existence of trimeric molecules was not contradicted by vibrational spectroscopic analysis of gallium trichloride saturated vapor.     

Mathematical model of creep for a microinhomogeneous nonlinearly elastic material

A mathematical model is proposed to describe the experimentally observed creep effect on the instantaneous elastic deformation of physically nonlinear elastic microinhomogeneous materials. Using a structural model of the medium, it is shown that, during unloading of a sample after creep at constant stress, the elastic strain can be both larger and smaller than the elastic strain during loading. It is shown that calculation results for a biocomposite material are in good agreement with experimental data. __________ Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 49, No. 3, pp. 157–163, May–June, 2008.     

Synthesis and Evaluation of a Macrocyclic Actinium-225 Chelator,Quality Control and In Vivo Evaluation of 225Ac-crown-αMSH Peptide

Targeted alpha-therapy (TAT) has great potential for treating a broad range of late-stage cancers by delivering a focused and lethal radiation dose to tumors. Actinium-225 (²²⁵Ac) is an emerging alpha emitter suitable for TAT; however, the availability of chelators for Ac remains limited to a small number of examples (DOTA and macropa). Herein, we report a new Ac macrocyclic chelator named ‘ crown’ , which binds quantitatively and rapidly (<10 min) to Ac at ambient temperature. We synthesized ²²⁵Ac- crown -αMSH, a peptide targeting the melanocortin 1 receptor (MC1R), specifically expressed in primary and metastatic melanoma. Biodistribution of ²²⁵Ac- crown -αMSH showed favorable tumor-to-background ratios at 2 h post injection in a preclinical model. In addition, we demonstrated dramatically different biodistrubution patterns of ²²⁵Ac- crown -αMSH when subjected to different latency times before injection. A combined quality control methodology involving HPLC, gamma spectroscopy and radioTLC is recommended.