Cobalt(II) porphyrin axially coordinated with 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-ylmethyl)-2′,4′-dihydro-1′H-pyrrolo[3′,4′ : 1,2](C60-Ih)[5,6]fullerene: formation,chemical structure,and spectroscopic properties

Construction of new effective photovoltaic devices based on organic dyes has important implications for modern and future technologies. In this article, we studied the equilibrium, the rate, and the spectral manifestation of the reaction of [(2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(2-pyridyl)porphyrinato)cobalt(II)]–[2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-ylmethyl)-2′,4′-dihydro-1′H-pyrrolo[3′,4′ : 1,2](C₆₀-I_h)[5,6]fullerene] triad formation as well as its spectral properties and photo electrochemical behavior. The cobalt porphyrin–pyridyl-substituted fullerene mixtures in toluene are self-assembling systems due to axial donor–acceptor binding between Co of the porphyrin complex and N-pyridyl of the substituted fullerene. The formation rate constant, k^298K, and the stability constant, K^298K, of donor–acceptor triad formed by coordination of two substituted fullerene molecules to Co porphyrin are (44.4 ± 0.8) mol L^?1 s^?1 and (56 ± 16)×10⁷ L² mol^?2, respectively. Modification of the titanium electrode coated with the natural oxide film was carried out using the porphyrin–fullerene triad and its individual components. Photopotential and photocurrent density of the system with modified electrode were studied. The obtained results are of interest for creating porphyrin-based donor–acceptor systems as components in organic photovoltaics.     

Cyanoacetylene and Its Derivatives: XXXI. Nucleophilic Addition of 2- and 4-Mercaptopyridines to Cyanacetylenes

Reactions of nucleophilic addition of 2- and 4-mercaptopyridines to 3-phenyl-2-propynonitrile, 4-hydroxy-4-alkyl-2-alkynonitriles, and methyl 2-butynoate (triethylamine, 20-25 or 100°C) give rise to the corresponding S-adducts with Z-configuration (for cyanoethylenes), or to a mixture of E- and Z-isomers in 60:40 ratio for methyl 2-butynoate.     

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf₂ containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around ?40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at ?91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of ?19.3°C forms upon slow cooling.     

Conductivity and electrochemical stability of concentrated aqueous choline chloride solutions

Russian Journal of Physical Chemistry A - The conductivity and electrochemical stability of choline chloride (ChCl) solutions with water contents ranging from 20 to 39 wt % are studied. Exposing...     

Electrochemical behavior of copper in 1-butyl-3-methylimidazolium bromide-copper(II) bromide binary ionic liquid

The methods of potentiometry, voltammetry, and gravimetry are used to study the electrochemical behavior of copper in the BMImBr-CuBr₂ ionic liquid (0?C30.5 mol % CuBr₂). It is shown that electrochemical reduction of copper(II) occurs irreversibly, in two one-electron stages (transfer coefficient ?? of the cathodic process are 0.58 and 0.46, accordingly, for the first and second stages). Diffusion coefficients of copper-containing ions D _Cu(II) at 60°C are 1.3 × 10^?7 and 1.6 × 10^?7 cm² s^?1 in melts with the CuBr₂ concentration of 0.1 and 1.5 mol kg^?1 of BMImBr, accordingly. High (up to 98%) deposition efficiency and high-quality copper deposit can be obtained in the potential range of ?2.0 to ?1.8 V (vs. a platinum quasireference electrode). It is found that the copper corrosion rate grows at an increase in the CuBr₂ concentration in the binary melt and is comparable with that in aqueous solutions of H₂SO₄-CuSO₄.     

Donor–Acceptor Complexes of (5,10,15,20-Tetra(4-methylphenyl)porphyrinato)cobalt(II) with Fullerenes C60: Self-Assembly,Spectral, Electrochemical and Photophysical Properties

The noncovalent interactions of (5,10,15,20-tetra(4-methylphenyl)porphinato)cobalt(II) (CoTTP) with C₆₀ and 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC₆₀) were studied in toluene using absorption and fluorescence titration methods. The self-assembly in the 2:1 complexes (the triads) (C₆₀)₂CoTTP and (PyC₆₀)₂CoTTP was established. The bonding constants for (C₆₀)₂CoTTP and (PyC₆₀)₂CoTTP are defined to be (3.47 ± 0.69) × 10⁹ and (1.47 ± 0.28) × 10¹⁰ M⁻², respectively. ¹H NMR, IR spectroscopy, thermogravimetric analysis and cyclic voltammetry data have provided very good support in favor of efficient complex formation in the ground state between fullerenes and CoTTP. PyC₆₀/C₆₀ fluorescence quenching in the PyC₆₀/C₆₀–CoTTP systems was studied and the fluorescence lifetime with various CoTTP additions was determined. The singlet oxygen quantum yield was determined for PyC₆₀ and the intensity decrease in the ¹O₂ phosphorescence for C₆₀ and PyC₆₀ with the CoTTP addition leading to the low efficiency of intercombination conversion for the formation of the ³C₆₀* triplet excited state was found. Using femtosecond transient absorption measurements in toluene, the photoinduced electron transfer from the CoTTP in the excited singlet state to fullerene moiety was established. Quantum chemical calculations were used for the determination of molecular structure, stability and the HOMO/LUMO energy levels of the triads as well as to predict the localization of frontier orbitals in the triads.     

Photoelectrochemical properties of thin films on titanium obtained by thermal,electrochemical, or sol-gel method

Journal of Solid State Electrochemistry - The photosensitivity of the titanium dioxide films on titanium substrate formed by the electrochemical, thermal, or sol-gel method was compared under the...     

The Temperature Effect on the Transport Properties of 1-Alkyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquids

The temperature dependences of specific and equivalent conductivities, viscosity, density, and crystallization temperature are determined for three 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C _n MeIm] [Tf₂N], n = 2, 3, 4) ionic liquids saturated with water vapor at room temperature. It is established that in the area of positive temperatures, the relationship between viscosity and conductivity obeys the fractional Walden rule with exponents of 0.97, 0.92, and 0.92 for ionic liquids with ethyl-, propyl-, butylradicals, respectively. The temperature dependences of conductivity and viscosity are approximated using the Vogel–Fulcher–Tammann equation (R² > 0.999), and ideal glass transition temperatures T₀ are calculated for the investigated liquids. The obtained values of T₀ depend largely on the chosen range of temperatures. It is shown that [C₂MeIm][Tf₂N] occupies a separate position with regard to [C₃MeIm][Tf₂N] and [C₄MeIm][Tf₂N].     

Structure-activity studies of irumamycin type macrolides from Streptomyces sp. INA-Ac-5812

Three natural glycosylated macrolide compounds, known irumamycin 1 and X-14952B 2, as well as new isoirumamycin 3, were isolated from ethyl acetate mycelium extract of Streptomyces sp. INA-Ac-5812. Structures of the compounds were elucidated using 1D and 2D NMR. Isoirumamycin 3 was found to be an isomer of irumamycin with an 18-membered macrolactone ring instead of 20-membered macrolide in irumamycin. A previously unknown stereo configuration of irumamycin epoxide (C23, C24) and hemiketal (C3, C7) fragments was deduced from NMR data (ROESY/NOESY and HSQMBC). Cytotoxic, antifungal and antibacterial activities were studied for all isolated compounds. Comparison of the collected data showed crucial importance of 20-membered macrolactone ring for antimicrobial properties of this antibiotic family.