Phthalocyanines prepared from 4-chloro-/4-hexylthio-5-(4-phenyloxyacetic acid)phthalonitriles and functionalization of the related phthalocyanines with hydroxymethylferrocene

The phthalonitrile derivative chosen for the synthesis of substituted phthalocyanines [M: 2H, Zn(II), Co(II)] with four chloro and four phenyloxyacetic acid substituents on the periphery is 4-chloro-5-(4-phenyloxyacetic acid)phthalonitrile. The sodium salt of carboxyl substituted zinc phthalocyanine is good soluble in water. Further reactions of zinc and cobalt phthalocyanines bearing phenyloxyacetic acid with thionylchloride gave the corresponding acylchlorides. This functional group reacted with hydroxymethylferrocene in dry DMF to obtain ferrocenyl substituted phthalocyanines. Also chloro substituent in new phthalonitrile was substituted with hexylsulfanyl substituent and its cyclotetramerization in the presence of Zn(AcO)₂·2H₂O and 2-(dimethylamino)ethanol resulted with zinc phthalocyanine. The compounds have been characterized by elemental analysis, MALDI-TOF mass, FT-IR, ¹H NMR, UV-Vis and fluorescence data. Aggregations properties of phthalocyanines were investigated at different concentrations in tetrahydrofuran, dimethylformamide, dimethylsulfoxide, water, and water/ethanol mixture. Also fluorescence spectral properties are reported.     

Electrochemical characterization of Co(II) and Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents

In this study, electrochemical behaviors of Co(II) and Pd(II) phthalocyanines carrying tetrakisdiethoxymalonyl and Pd(II) phthalocyanine carrying tetrakiscarboxymethyl substituents at the peripheral positions are investigated by cyclic voltammetry and applied potential chronocoulometry techniques. Cyclic voltammetric studies show that, while Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents give up to three common phthalocyanine ring reductions, Co(II) phthalocyanine carrying diethoxymalonyl substituents gives a metal-centered oxidation and a metal-centered reduction and three ligand-centered reduction and a ligand-centered oxidation processes. First reduction processes of both the PdPc complexes have shoulders. This different voltammetric behaviors of Pd(II) phthalocyanines carrying carboxymethyl and diethoxymalonyl substituents results from interaction of this distinctive substituents with the phthalocyanine ring π electron system and interaction with the different solvent systems. Observation of the splitting of the first reduction process of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents suggests the aggregation of the complex. Very small diffusion coefficient of the complexes with respect to Co(II) phthalocyanine also confirms the existence of the aggregation of the complex during the electrochemical studies. Effects of the substituents and the solvent media are clearly observed from the differences of the voltammograms of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents in DMSO and THF solvent media, respectively. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 1, pp. 36–43. The text was submitted by the authors in English.     

Synthesis,electrochemistry and in situ spectroelectrochemistry of water-soluble phthalocyanines

The synthesis, characterization and voltammetric and spectroelectrochemical properties of newly synthesized metal-free and metallo phthalocyanines (M = Co, Cu, Zn) containing four dialkylaminophenoxy or trialkylammoniumphenoxy substituents on peripheral positions have been presented in this work. The new compounds have been characterized by using elemental analysis, UV–Vis, FT-IR, ¹H NMR and MS spectroscopic data. Phthalocyanines with trialkylammoniumphenoxy substituents are soluble in aqueous solution over a wide pH range, and these compounds are present as aggregated species in solution as confirmed by the blue shift of Q-bands in their electronic spectra. The electrochemical behavior of the phthalocyanines was investigated by cyclic voltammetry and differential pulse voltammetry on a platinum-working electrode in DCM and DMSO. The voltammetric and spectroelectrochemical measurements of the complexes show that while cobalt phthalocyanine gives both ligand- and metal-based redox processes, metal-free, zinc and copper phthalocyanine complexes give only ligand-based processes in harmony with common phthalocyanine complexes.     

Synthesis and liquic crystalline properties of copper tetra-4-(n-alkoxycarbonyl)phthalocyanines

Copper tetra-4-(n-alkoxycarbonyl)phthalocyanines were synthesized, and their thermotropic and lyotropic mesomorphism at different lengths of lateral substituents was studied. Their possibility of forming both thermotropic and lyophilic mesophases (amphotropy) was found. The length of lateral substituents affects the type of supramolecular packing in the mesophase rather than the temperature of the crystal→mesophase phase transition. A rarecase of the mesogeneity of disk-like compounds of the same chemical nature possessing only four substituents is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 129–136, January, 2000.     

Synthesis and liquic crystalline properties of copper tetra-4-(n-alkoxycarbonyl)phthalocyanines

Copper tetra-4-(n-alkoxycarbonyl)phthalocyanines were synthesized, and their thermotropic and lyotropic mesomorphism at different lengths of lateral substituents was studied. Their possibility of forming both thermotropic and lyophilic mesophases (amphotropy) was found. The length of lateral substituents affects the type of supramolecular packing in the mesophase rather than the temperature of the crystal→mesophase phase transition. A rarecase of the mesogeneity of disk-like compounds of the same chemical nature possessing only four substituents is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 129–136, January, 2000.     

Structure and proton donating ability of 2- and 2,5-bis(1-trifluoromethanesulfonylamido-2,2,2-trichloroethyl)pyrroles

2-(1-Trifluoromethanesulfonylamido-2,2,2-trichloroethyl)pyrrole and 2,5-bis(1-trifluoromethanesulfonylamido-2,2,2-trichloroethyl)pyrrole according to quantum chemical calculations (B3LYP/6-311G**) exist in the isomeric forms whose structure determines the formation of intramolecular hydrogen bonds NH⋯Cl, NH⋯O=S and CH⋯O=S of different strength. Potentiometric and spectroscopic acidity of these compounds is determined. From the data of IR spectroscopy their proton donating ability upon interaction with Lewis bases is shown depending on the presence of intramolecular hydrogen bonds, mutual effects of intermolecular hydrogen bonds formed by the sulfonamide and pyrrole NH groups with the base, and electronic effects of the substituents. Original Russian Text ? L.P. Oznobikhina, N.N. Chipanina, B.A. Shainyan, L.V. Sherstyannikova, V.A. Kukhareva, T.N. Aksamentova, E.V. Kondrashov, G.G. Levkovskaya, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 2, pp. 326–333.     

Structure of 2-chloro-3-phenylbenzoic acid

The carbonylation reaction of 2,3-dichlorobiphenyl proceeds with a substitution of the chlorine atom in position 3 and results in the formation of 2-chloro-3-phenylbenzoic acid. The structure of this acid is revealed by single crystal XRD. It is determined by steric interactions of substituents in positions 2,4,2′, and 6′, a stable carboxyl supramolecular synthon, and weak interactions with the participation of the carbonyl oxygen atom and the chlorine atom. Original Russian Text Copyright ? 2009 by V. P. Boyarskiy, M. S. Fonari, K. Suwinska, and Yu. A. Simonov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 3, pp. 605–607, May–June, 2009.     

A novel route for the synthesis of composite dielectric core/silver shell particles

We demonstrated the possibility of preparing continuous silver shells on particles of polystyrene latex by enlarging adsorbed seeding metal nanoparticles in solution containing ascorbic acid and silver nitrate. It is shown that a strong batochromic shift of the maximum of surface plasmon resonance is observed for such composite structures. Original Russian Text ? O.V. Dement’eva, M.A. Filippenko, M.E. Kartseva, V.M. Rudoy, 2009, published in Kolloidnyi Zhurnal, 2009, Vol. 71, No. 4, pp. 569–571.     

Zinc-cobalt alloy: electrodeposition and characterization

Zinc-cobalt alloy electrodeposits offer enhanced corrosion protection to steel, compared to zinc deposits. A near neutral zinc-cobalt alloy sulfate bath was developed. In the absence of β-naphthol and sodium lauryl sulfate (SLS), only a light grey and non-uniform deposit was obtained. Addition of boric acid yielded a grey and uniform deposit. To obtain the grey uniform alloy deposit, the optimum bath composition was: 0.5 M ZnSO₄, 0.5 M CoSO₄, 40 g/L H₃BO₃, 0.865 g/L SLS and 0.345 g/L β-naphthol. The current efficiency for alloy deposition was 50% in the current density range 0.5–2.5 A/dm². X-ray fluorescence studies on the alloy deposit formed on steel revealed 58–75% zinc on the surface. Anodic stripping voltammetric studies were carried out on zinc-cobalt alloy films formed on glassy carbon to identify the phases formed in the alloy. Zn-Co alloy film dissolution peaks suggested the existence of β, β₁ and γ phases of the alloy. Electronic Publication     

Aggregative Properties of Water-soluble Metal Phthalocyanines in a Borate Buffer Solution

Thermodynamic characteristics of dimerization of water-soluble zinc, copper, and cobalt complexes of sulfo- and carboxy-substituted phthalocyanines were obtained. A correlation of the aggregative capacity of the metal phthalocyanines with the nature of the central metal atoms and the number and position of peripheral substituents was revealed.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 683–688.Original Russian Text Copyright © 2005 by Lebedeva, Pavlycheva, V’yugin, Davydova, Maizlish, Shaposhnikov.     

The heat capacity of the ethylene glycol-tetrahydrofuran system over the range of tetrahydrofuran concentrations 0–20 mol %

The heat capacity of the ethylene glycol (EG)-tetrahydrofuran (THF) system was measured over the range of THF concentrations 0–20 mol % and the temperature range 0–50°C using a DSC204FI differential scanning calorimeter. It was found that the heat capacity passed through a maximum at a THF concentration of 5 mol %; the maximum became more pronounced as the temperature increased. It was suggested that the maximum was caused by microphase separation at THF concentrations of 5–10 mol %. We were unable to observe phase separation with the lower critical point visually over this concentration range up to 95°C. Original Russian Text ? M.N. Rodnikova, D.B. Kayumova, L.A. Tsvetkova, I.A. Solonina, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1196–1198.     

Investigation of azomethine group vibrations in aromatic schiff bases and their N-oxides by vibrational spectroscopy methods

The effects of fluorine substitution in benzene rings and quaternization of the nitrogen atom in Schiff bases of the general formula R−CH=N−R′ on the vibration characteristics of the azomethine group are analyzed. Normal vibrations and intensities of IR bands are calculated. It is shown that the spectroscopic behavior of the C=N bond is almost independent of the electronic effects of substituents in the benzene rings of the molecules studied, and the changes in the intensities of ν_C=N bands are caused by interactions between vibrations. This points to the stability of this bond in the series of molecules under consideration. For diphenylnitrones, N→O vibrations are identified. L. M. Litvinenko Institute of Physical Organic Chemistry and Carbon Chemistry. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 2, pp. 310–315, March–April, 1995. Translated by L. Smolina     

On the oscillatory character of the sorption of amino acids on cationites

The kinetics of the absorption of D,L-β-phenyl-α-alanine and L-tryptophan by KU-2 × 8 sulfocationite was studied by spectrophotometry, dilatometry, and microscopy. Contrary to the literature data, the oscillatory character of absorption was not observed. Original Russian Text ? M.P. Tsyurupa, L.A. Pavlova, A.V. Pastukhov, V.A. Davankov, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 5, pp. 996–999.     

Chain-length-identification strategy in zinc polyphosphate glasses by means of XPS and ToF-SIMS

The surface chemistry of amorphous zinc polyphosphates of different compositions (ranging from zinc metaphosphate to zinc orthophosphate) has been investigated by means of X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary-ion mass spectroscopy (ToF-SIMS). The identification of the chain length of zinc polyphosphates by XPS was on the basis of the integrated intensity ratio of the bridging (P–O–P) and nonbridging (P = O and P–O–M) oxygen peaks used for fitting the oxygen 1s signal, the shift of the P 2p_3/2 signal towards lower binding energies and the modified Auger parameter towards higher values as the zinc content increases. The discrimination of the polyphosphate chain lengths was also achieved by ToF-SIMS, by comparing the intensities of selected characteristic phosphate fragments. Both techniques appear to be suitable for the investigation of polyphosphate glasses in applications such as tribology, where there is a need to identify the chain length present in the outermost monolayer of the film. Fourier-transform infrared (FT-IR) spectroscopy was used to characterize the bulk compounds. The FT-IR studies showed that long-chain structures linked through P–O–P bonds predominate in the metaphosphate composition, while when the zinc content is increased, the chains become shorter, ultimately being replaced by PO₄ monomers in the orthophosphate composition.     

Non-linear correlations between formal potential and Hammett parameters of substituted iron phthalocyanines and catalytic activity for the electro-oxidation of hydrazine

The activity of the different iron phthalocyanines was examined using the complexes adsorbed on graphite electrodes. The effect of the Fe(II)/(I) formal potential of iron phthalocyanines on the their catalytic activity for the electro-oxidation of hydrazine was investigated. A plot of log k (rate constant at constant potential) versus the Fe(II)/(I) formal potential gives a volcano curve. The rate of the reaction increases with the driving force of the catalyst (measured as its formal potential) and then decreases for higher driving forces. A similar graph is obtained with a plot of log k versus the sum of the Hammett parameters of the substituents on the periphery of the phthalocyanine ligand. A maximum activity is obtained for a complexes having an M(II)/(I) redox potential close to –0.6 V which agrees with previous studies conducted with phthalocyanines of different metals and with cobalt phthalocyanines bearing different substituents.Dedicated to Prof. Wolf Vielstich on the occasion of his 80th birthday in recognition of his numerous contributions to interfacial electrochemistry.     

The complex formation properties of 18-crown-6-2-styrylbenzothiazole and the product of its photocyclization

Complex formation of 18-crown-6-2-styrylbenzothiazole and a crown-containing benzothiazolquinoline derivative with alkaline earth metal perchlorates was studied. The structures and stability constants of the complexes were determined. Original Russian Text ? O.A. Fedorova, E.N. Gulakova, I.E. Lobazova, Yu.V. Fedorov, N.E. Shepel’, L.G. Kuz’mina, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1178–1182.     

The influence of a competing eluting ion content on the efficiency of separation of rare-earth metals in displacement complex forming chromatography

The separation of rare-earth metals (REMs) by displacement complex forming chromatography was studied for S-shaped isotherms of the eluting ion with eluted elements. It was found that sodium competing ions, which entered the REM zone, decelerated ion exchange of REMs. The effect increased as the amount of eluting ions entering the zone of elements to be separated grew. Original Russian Text ? O.V. Kharitonov, L.A. Firsova, E.A. Chuveleva, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1169–1170.     

Determination of zinc(II) and cadmium(II) as their complexes with Xylenol Orange by capillary elecrophoresis using online preconcentration

A new version of online preconcentration employing the pH-stacking mechanism has been proposed; it has been implemented by the example of a procedure for the capillary electrophoretic determination of trace zinc(II) and cadmium(II) with photometric detection in the visible spectrum region as complexes with Xylenol Orange. The analytical range is 2–400 μg/L for zinc(II) and 1–500 μg/L for cadmium(II).     

Effect of styryl substituents introduced into the periphery of pyrazinoporphyrazine macrocycle on the spectral and luminescence properties of complexes

A synthesis is reported for a new pyrazinoporphyrazine complex containing eight styryl fragments on the periphery of the macrocycle, namely, zinc tetrakis-2,3-{5,6-bis[(E)-2-(4-methylphenyl)vinyl]pyrazino}-porphyrazine. The introduction of styryl substituents into the macrocycle leads to a significant bathochromic shift of the Q-band in the electronic absorption spectrum and to an increase in the fluorescence quantum yield. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 2, pp. 118–123, March–April, 2007.     

Thermodynamic characteristics of complex formation in the nickel(II) ion-β-alanine systems in aqueous solution

Heats of reactions between a nickel(II) ion and β-alanine were measured calorimetrically at 288.15, 298.15, and 308.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). Thermochemical data were processed with account for stepwise equilibria; attendant protolytic processes were taken into account together with complexing reactions. Extrapolation to the zeroth ionic strength with the use of a one-parameter equation gave standard thermodynamic characteristics of complex formation in the system. The influence of the supporting electrolyte and temperature on the heats of complex formation reactions was considered. Standard enthalpies of formation were calculated for NiAla⁺, NiAla₂, and NiAla₃⁻ species. Original Russian Text ? L.A. Kochergina, O.V. Platonycheva, O.M. Drobilova, V.V. Chernikov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 2, pp. 377–384.