Magnesium octa[(4′-benzo-15-crown-5)oxy]phthalocyaninate in water micellar solutions of sodium deoxycholate

Aggregation of magnesium octa-[(4′-benzo-15-crown-5)oxy]phthalocyaninate (Mgcr₈Pc) in solutions of biocompatible anionic surfactant, sodium deoxycholate (SDC), was studied. It was shown using the electron absorption spectra that formation of Mgcr₈Pc monomers in micellar solutions of SDC is affected by both increased surfactant concentration and by changes in the ionic strength of solution after sodium chloride is added. The effect of the chemical structure of biocompatible anionic surfactant on monomerization of crown-containing phthalocyanines was identified; this fact opens new possibilities for using this family of compounds for fluorescent diagnosis and photodynamic therapy.     

Octa- and tetra-(benzo-15-crown-5)phthalocyanines in surfactant-containing solutions

The behavior of octa-(benzo-15-crown-5)phthalocyanine (H₂cr₈Pc), as well as cobalt octa- and tetra-(benzo-15-crown-5)phthalocyaninates (Cocr₈Pc and Cocr₄Pc), in aqueous solutions containing cationic or anionic surfactants, such as cetyl trimethylammonium bromide (CTAB), sodium carboxymethyl cellulose (Na-CMC), and sodium dodecyl sulfate (SDS), is studied using electronic spectroscopy. The presence of eight benzo-15-crown-5 ether fragments on the periphery of the phthalocyanine ring is shown to facilitate the dissolution of Pc in an aqueous environment. The interactions between CTAB and crown-containing Pc promotes the dissolution of H₂cr₈Pc; Cocr₈Pc; and, to a lesser degree, Cocr₄Pc, which is accompanied by the appearance of molecular aggregates, including heteronuclear cofacial dimers. The presence of a metal in the ring is not the necessary condition of the process. In microscopically heterogeneous medium, such as an aqueous SDS-containing solution, H₂cr₈Pc is present in monomeric form at SDS concentrations close to C _cr and in dimeric form at SDS content below C _cr. Under similar conditions (environment, surfactant), Cocr₄Pc can exist in monomeric form at SDS concentrations much high than C _cr. The effect of the size of cation on the form of the crown-containing Pc in an aqueous solution is illustrated by an example of H₂cr₈Pc. Na-CMC promotes the dissolution of Pc and enables one to produce K⁺/Mcr₈Pc-modified films from aqueous solutions.     

Comparison of photophysicochemical properties of hexaphenoxycyclotriphosphazenyl-substituted metal-free,mono- and bis-lutetium phthalocyanines

The aim of this study is to compare the photophysicochemical properties of hexaphenoxycyclotriphosphazenyl-substituted metal-free (1), mono-(phthalocyaninato) lutetium(III) (2) [Lu^III(AcO)(Pc)] (Pc = phthalocyaninato, AcO = acetate) and bis-(phthalocyaninato) lutetium(III) (3) [Lu^IIIPc₂]. The synthesis and characterization (using the elemental analysis, mass spectrometry, IR, ¹H, and ³¹P NMR and UV–vis spectroscopy) of new compounds (2, 3) are described in this study. The electronic absorption and fluorescence spectral properties of compounds 1–3 are investigated. Photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) measurements are also studied on hexaphenoxycyclotriphosphazenyl-appended metal-free, mono- and bis-lutetium phthalocyanines in dimethylsulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanines are very useful for photodynamic therapy (PDT) applications. Singlet oxygen quantum yields (Φ_Δ) give an indication of the potential of the complexes as photosensitizers in PDT applications. Hexaphenoxycyclotriphosphazenyl-substituted mono-(phthalocyaninato) lutetium(III) complex (2) gave good singlet oxygen quantum yield (0.66) in DMSO. Thus, this complex shows potential as Type II photosensitizer for PDT of cancer.     

New tetra- and octa-functionalized phthalocyanines: Methods of synthesis and physicochemical properties in aqueous solutions and on solid substrates. Review

Methods of synthesis of a number of new functionalized phthalocyanines, as well as Mg^II, Co^II, Cu^II, Zn^II, and Ni^II phthalocyaninates, that involve benzo-15-crown-5-, phosphoryl-, or pyridine-containing fragments as peripheral substituents, which were developed and tested in IPCE RAS in the last five years, are reviewed and systematized. Methods of synthesis of the original phthalogens, which involve substituents of diverse composition, are considered. Results of an investigation of the aggregate states of the compounds in water and aqueous solutions of salts are generalized. The possibilities of electrostatic immobilization of the synthesized phthalocyanines in the form of self-assembled systems composed of ultrathin ionic layers on quartz and conductive glasses are considered. Based on the spectral, electrochemical, and electrocatalytic properties, the role of noncovalent interactions in the synthesis and operation of the composite systems is clarified.     

Heteroleptic triple-decker terbium(III) (porphyrinato)(crownphthalocyaninate) as an efficient receptor of alkaline metal cations

Peculiarities of the interaction between a heteroleptic triple-decker terbium(III) complex of a general type [Br₄TPP]Tb[(15C5)₄Pc]Tb[(15C5)₄Pc] (Tb-TD*, where Br₄TPP = 5,10,15,20-tetra-(4-bromophenyl)-porphyrin and (15C5)₄ Pc = tetra-(15-crown-5)-phthalocyanine) and potassium cations in different solvents are studied. The interaction between Tb-TD* and potassium acetate is found to proceed via either the supramolecular dimerization of the complex or the inclusion of the cations between the crown-containing molecular decks depending on the polarity of the media. From the analysis of the titration curves, the stability constant of Tb-TD* × 4K⁺ adduct in a chloroform : methanol = 1 : 1 mixture was estimated. The stability constant of the aggregate was found to exceed the known values of similar compounds by over ten orders.     

Synthesis, photophysical and photochemical properties of crown ether substituted zinc phthalocyanines

The photophysical and photochemical properties of the tetra- and octa-12-crown-4-substituted zinc (II) phthalocyanines are reported for the first time in the scope of this work. The new compounds have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in dimethylsulphoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for photodynamic therapy (PDT) applications. The effects of the substituents on the photophysical and photochemical parameters of the zinc (II) phthalocyanines (5, 6 and 7) are also reported. The singlet oxygen quantum yields (Φ_Δ) ranged from 0.48 to 0.78 are indicating the potential of the complexes as photosensitizers in applications of PDT. The fluorescences of the substituted ZnPc complexes are effectively quenched by benzoquinone (BQ).     

Preparation,characterization, electrochemistry and in situ spectroelectrochemistry of novel α-tetra[7-oxo-3-(2-chloro-4-fluorophenyl)coumarin]-substituted metal-free,cobalt and zinc phthalocyanines

In this study, a novel ligand, 7-(2,3-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin was synthesized by the reaction of 3-(2-chloro-4-fluorophenyl)-7-hydroxycoumarin with 1,2-dicyano-3-nitrobenzen in dry DMF as the solvent in the presence of K₂CO₃ as the base. The preparation of the corresponding phthalocyanines H₂Pc, CoPc and ZnPc, substituted with 7-oxo-3-(2-chloro-4-fluorophenyl)coumarin functional groups at α positions of the Pc ring, was achieved by the cyclotetramerization of the coumarin ligand without any metal salts or with the relevant metal(II) acetates in 2-N,N-dimethylaminoethanol. The structures of the compounds were confirmed by elemental analysis, UV–vis, IR, MALDI-TOF mass and ¹H NMR spectra. In addition, aggregation and redox properties of the novel phthalocyanines with four halogenated coumarinoxy substituents at α positions of the phthalocyanine ring were compared with those of previously reported corresponding ones with β-substitution, by UV–vis spectroscopy, in situ spectroelectrochemistry and voltammetry. Remarkable differences in these properties between α- and β-substituted compounds were detected, and discussed in detail.     

Investigation of crown-containing styrylthiophene derivatives which are optically and electrochemically sensitive to the presence of metal cations

The analysis of complex formation of crown-containing styryl and bisstyryl thiophene derivatives with alkaline earth metal cations and the investigation of optical and electrochemical responses induced by metal cations are reported. The monostyryl derivative forms weakly fluorescent inclusion complexes with Mg²⁺ cations and weakly fluorescent anti-sandwich complex with Ba²⁺ cations. In case of bisstyryl thiophene compounds the Mg²⁺ complexes are fluorescent, whereas, the sandwich complex with composition (1b)₂·(Ba²⁺)₂ or (1b)₂·(Ba²⁺)₃ are weakly fluorescent. The results of the investigations showed that the crown-containing mono- and bisstyryl thiophene derivatives are optically and electrochemically sensitive to the presence of metal cations.     

无金属酞菁、酞菁铜和酞菁锌在1 mol/L H2SO4中对Q235钢的缓蚀作用

通过失重实验、电化学测试和扫描电子显微镜研究了无金属酞菁(H2Pc)、酞菁铜(CuPc)和酞菁锌(ZnPc) 在1 mol/L H2SO4中对碳钢的缓蚀作用.结果表明,3种酞菁化合物的缓蚀能力依次为ZnPc > CuPc > H2Pc,其吸附数据均符合Langmuir等温式;它们能同时抑制碳钢在H2SO4中腐蚀的阴极和阳极过程,电化学阻抗谱显示,为变形的单容抗弧,阻抗值随酞菁化合物浓度增加而增加;表面形貌分析也证明了酞菁化合物的加入提高了碳钢的表面完整性,抑制其腐蚀;量子化学计算结果显示,随着分子的最低空轨道(LUMO)的能量升高,酞菁化合物的缓蚀能力降低.     

Solubilization of Crown-Substituted Magnesium Phthalocyaninates in Solutions of Salts of Bile Acids

Crown-containing Pc Mg[(B15C5O)₈Pc], Mg[(B15C5O)₄Pc], and Mg[(15C5)₄Pc] are in the monomolecular state in solutions of synthetic anionic surfactants: sodium dodecylsulfate and sodium dodecylbenzenesulfonate. In micellar solutions of bile-acid salts, molecular organization of crown-substituted Pc with different methods of introduction of crown groups into the macrocycle and their different numbers changes their state from predominantly monomeric for Mg[(B15C5O)₈Pc] in the presence of NaCl to the aggregated one in the case of Mg[(15C₅)₄Pc)]. Magnesium phthalocyaninate with annulated (15-crown-5)-fragments, Mg[(15C₅)₄Pc], is characterized by the highest sensitivity to the structure of the micelle-forming biocompatible surfactant.     

Photoisomerization of crown-containing styrylbenzothiazole and styrylquinoline in complexes with hydroxypropyl-β-cyclodextrin

The investigation of host-guest interactions of crown-containing styrylbenzothiazole and styrylquinoline with 2-hydroxypropyl-β-cyclodextrin in aqueous media were carried out by means of electronic absorption and fluorescence spectroscopy, 1D and 2D NMR. UV irradiation was used for photochemical transformation of complexes. It was found that the photochemical transformation of supramolecular complexes includes E-Z photoisomerization of guest molecules.     

New conductive polymeric materials: Cofacial assembly of mixed valent metallomacrocycles

This paper reports on an approach to control molecular stacking interactions in low-dimensional mixed valence materials by locking partially oxidized metallomacrocycles together in a cofacial orientation. Iodine doping of the face-to-face linked oligomers [M(Pc)O]_n (M = Si, Ge, Sn; Pc = phthalocyaninato) produces electrically conductive polymers {[M(Pc)O]I_xn with a wide range of x stoichiometries. Resonance Raman spectroscopy indicates that the iodine has oxidized the polymer chain. Polymer structure has been studied by X-ray powder diffraction, and it is possible to estimate interplanar spacings. Halogen doping of the [M(Pc)O]_n materials is accompanied by electrical conductivity increases as large 10⁷ (ohm cm)^?1; the general trend is $\text{σ}{}_{\mathrm{<mtext>Si</mtext>}}\text{? σ}{}_{\mathrm{<mtext>Ge</mtext>}}\text{> σ}{}_{\mathrm{<mtext>Sn</mtext>}}$. Variable temperature conductivity and magnetic susceptibility data are reported.     

Physicochemical properties of solutions and ultrathin films of triple-decker gadolinium tetra-15-crown-5-phthalocyaninate

The ability of the triple-decker gadolinium complex with tetra-15-crown-5-phthalocyanine Gd₂(R₄Pc)₃, (R = 15-crown-5) (1) to form monolayers and Langmuir-Blodgett films (LBFs) was studied for the first time. The charge characteristics of molecules of a triple-decker phthalocyaninate in monolayer, as well as their orientation and adhesion to the water subphase, were controlled by changing the surface pressure, pH, and subphase composition (aqueous solutions containing triethylenetetramine (TETA) and metal cations). It was shown that the presence of Na⁺ and protonated TETA aminogroups in resulted in an increasing limiting monolayer area and significant decreasing of the monolayer liquid state region. It is proven that the observed effects are caused by the conformational and charge transitions of peripheral crown ethers induced by their interaction with cations. A comparison of the differential reflectance spectra of the complex monolayer on the deionized water surface with UV-Vis absorption spectra of three-layer Gd₂(R₄Pc)₃ LBF and complex solution in chloroform shows that partial complex oxidation and intensive stacking formation occurs already at the stage of monolayer formation on the subphase surface. Electrochemical studies of three-layer LBFs performed at the indium-tin-oxide electrodes (ITO-electrodes) using cyclic voltammetry (CV) showed three reversible redox waves in the potential range −200 to +1100 mV (vs. Ag⁺/AgCl). All registered peaks remain the same position and intensity upon multiple cycling. plasmon resonance (SPR) measurements allow to register three stable redox states of studied LBF upon applying the external potential. Such behavior shows the possibility to use multistep redox transformations of studied complex LBF for developing of stable and reproducible switchable optoelectronic systems.     

Electrically conductive,processable polymeric materials constructed from metallophthalocyanines

This contribution describes an approach to producing new classes of macromolecular/macromolecular and molecular/macromolecular hybrid materials which can be spun into environmentally stable, flexible, oriented, electrically conductive fibers. Solutions of a phthalocyanine-containing macromolecular (e.g., [Si(Pc)O]_n) or molecular(e.g., Ni(Pc)) ‘metal’ precursor and a host polymer (e.g., Kevlar) are wet-spun to yield, after halogen or electrochemical doping, strong, air-stable fibers with thermally activated electronic conductivities as high as 5 ω^?1 cm^?1. X-ray diffraction and resonance Raman studies of the fibers reveal the presence of preferentially oriented Kevlar and {[Si(Pc)O]I_1.1}_n (or M(Pc)I) crystalline regions, the latter regions with the metallophthalocyanine stacking directions preferentially parallel to the longitudinal fiber axis.     

Complexes of zinc(II) tetra-(15-crown-5)-phthalocyaninate with axially coordinates N-donor ligands as potential components of photosensitive materials of telecommunication range

The methods of electron absorption spectroscopy and ¹H NMR were used to study the processes of interactions between zinc tetra-(15-crown-5)-phthalocyaninate and a number of N-donor ligands, including 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 3-aminopyridine, imidazole, 2-amino-5-methylpyridine, 2-methyla-4-aminopyridine, 2,3-diaminopyridine, pyrazine. A new effective method for synthesizing zinc tetra-15-crown-5-phthalocyaninate was developed that allowed one to obtain the complex at a yield of greater than 80% under simple conditions in 2 h. The structure of associates was studied in detail using the example of interactions between zinc tetra-15-crown-5-phthalocyaninate and 1,4-diazabicyclo[2.2.2]octane. ¹H NMR studies in a wide temperature range of 213–323 K (−60 to +50°C), as well as quantum-chemical calculations, allowed us to establish the formation of two types of associates of phthalocyanine and 1,4-diazabicyclo[2.2.2]octane with the composition of 1: 1 and 2: 1. Up to a temperature of 253 K, the 1: 1 and 2: 1 associates are in equilibrium with a high rate of interconversion.     

High resolution solid-state 13C CPMAS study of neutral and partially oxidized aluminium polyfluorophthalocyanines

This paper reports a high resolution solid-state ¹³C CPMAS study of the low dimensional phthalocyanine (Pc = C₃₂H₁₆N₈) conductors (PcAlF)-(MoF₆)_0.38, (PcAlF)(IF₅)_0.43 and (PcAlF)(XeF₂)_0.35 as well as the precursor (PcAlF)_n. This study confirms that the stacking configuration of Pc rings along polymeric chains of neutral polymer is eclipsed. The four inequivalent carbon sites resulting from this structure are clearly separate and identified. From this study it is concluded that intrachain disorder is more extended in MoF₆- and IF₅-doped compounds than in the XeF₂-doped one.     

Tetra(9,10-phenanthro)tetraazaporphyrin - phthalocyanine: Comparative electrical conductivities

Tetra(9,10-phenanthro)tetraazaporphyrin, H₂TPTAP, has been synthesized and characterized for comparative electrical conductivity measurements with phthalocyanine, H₂Pc, before and after iodine doping. The objective is to determine the effect on conductivity of fusing eight additional benzo rings to the periphery of the phthalocyanine ring. H₂Pc doped to a (H₂Pc)I_2.5 composition with a resistivity decreases from 10¹⁵ to 1 ω cm, while H₂TPTAP doped to a (H₂TPTAP)I_0.26 composition with a corresponding resistivity change from 10¹¹ to 10⁸ ω cm. Experimental data and the literature indicate that benzene rings fused to the periphery of the tetraazaporphyrin ring have little π-electron interaction. Similarly, the structure-conductivity correlation of data is interpreted as indicating that fusion of additional benzo rings has an insulating substituent group effect on oxidation of and charge transport between the tetraazaporphyrin rings in the polycrystalline solid.     

Synthesis,characterization and electrical and CO2 sensing properties of triazine containing three dendritic phthalocyanine

The metal-free phthalocyanine 1a was synthesised by statistically mixed condensation of 4-nitrophthalonitrile and 4-(2-dimethylaminoethylsulfanyl)phthalonitrile in dry 2-(dimethylamino)ethanol. The same route were applied to prepare metal-containing phthalocyanines using metal salts Zn(OAc)₃·2H₂O and CoCl₂, respectively, in dry DMF. The nitro compounds were reduced to amine with sodium sulfide and quarternized by reaction of MeI. These compounds were then reacted with cyanuric chloride in the presence of potassium carbonate as a base in mixture of THF and DMF gave s-triazine containing three amino phthalocyanines 4a–c. The reaction of three phthalocyanines with sodium salt of triethylmethanetricarboxylate in absolute ethanol were synthesised first generation of dendrimer 5a–c. The second generation of dendritic phthalocyanines 6a–c were prepared by the reaction of dentritic phthalocyanines with tris (H₂NC(CH₂OH)₃) using K₂CO₃ as a base in DMSO. The dendritic phthalocyanines containing tris are slightly soluble in water. The new compounds were characterized by elemental analysis and UV–vis, IR, NMR spectra. The temperature dependence of the dc and ac conductivity of these compounds and the adsorption of CO₂ gas on thin film of the compounds were investigated by dc conductivity and impedance spectroscopy technique using an interdigital transducer structure on glass substrate. While exposure to CO₂ have no influence on the electrical conductivity (ac and dc) of compound 6a and 6c, the conductivity of the film of 6b strongly depend on the presence of the CO₂ gas. Completely reversible sensor signals were obtained for compound 6b. The impedance spectra were obtained at frequencies between 40 and 10⁵ Hz, and in a wide range of CO₂ concentrations (from 500 to 8000 ppm) at room temperature. The temperature dependence of dc conductivity show typical Arrehenius behaviour for all compounds. The ac conductivity of the films is represented by the form ω^s. The dependency of frequency exponent s on temperature suggests a correlated barrier hopping (CBH).     

Novel `synthetic metals' based on symmetrically tetrasubstituted nickel phthalocyanines

Nickel(II) 2,9,16,23-tetrasubstituted phthalocyanines, NiPTX (where X=–OH, –NO₂, –NH₂ and –SO₃H) were synthesized in pure state and doped with iodine. Elemental analysis, UV-Vis, infrared, X-ray diffraction, magnetic susceptibility and TGA studies were used to investigate the effects of iodine doping as well as substituents on the properties of the complexes. The electrical conductivity of nickel phthalocyanine derivatives found to depend on the nature of the substituents and showed ∼10³–10⁵ times increased electrical conductivity in comparison to parent nickel phthalocyanine. Further, the substitution and iodine doping show remarkably very high improved electrical conductivity nearly 10¹¹ times the electrical conductivity of nickel phthalocyanine.     

Kinetics of phase transformations in the surface layer of a binary alloy at the selective dissolution: III. Cu-Au | Cu<Superscript>2+</Superscript> system

Conditions of the phase transformation of gold on the surface of Cu-Au alloys selectively dissolved in an acidic sulfate solution at the overcritical anodic polarization are experimentally found. Kinetic regularities of the formation of an individual Au⁰ gold phase on the alloy surface depending on the alloy composition, anodic potential, and the presence of organic surfactants in the solutions are determined.