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.     

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.     

Supramolecular assembly of sandwich-type heteroleptic lanthanum (porphyrinato)(phthalocyaninates)

Concentration and cation-induced supramolecular assembly of heteroleptic double- and triple-decker [An₄P]La[(15C5)₄Pc] and [An₄P]La[(15C5)₄Pc]La[An₄P] lanthanum complexes (An₄P²⁻ = 5,10,15,20-tetra-(4-methoxyphenyl)-porphyrinate dianion and(15C5)₄Pc²⁻ = tetra-(15-crown-5)-phthalocyaninate dianion) is studied. Double-decker [An₄P]La[(15C5)₄Pc] complex is shown to be susceptible to effective concentration-driven assembly determined by the deviation from the Beer-Lambert-Bouguer law up to a concentration of 10⁻⁶ M. Triple-decker [An₄P]La[(15C5)₄Pc]La[An₄P] complex is not inclined to the concentration-driven assembly up to a concentration of 10⁻⁴ M. The interaction between the receptors and sodium or potassium salt is determined by the receptor structure and independent of the salt anion. When interacting with potassium salts, the double-decker complex can form a supramolecular cofacial dimer. In the case of the triple-decker complex, the crown-phthalocyanine deck of the molecule is sterically blocked, and supramolecular aggregates do not form. Sodium cations can be encapsulated in the crown ether rings of both receptors.     

Photorefractive and nonlinear optical properties of indium(III) tetra(15-crown-5)phthalocyaninate-based composites

Photoelectric, nonlinear optical, and photorefractive properties of hybrid composite materials based on polyvinylcarbazole (PVK) and indium(III) 2,3,9,10,16,17,23,24-tetra(15-crown-5)phthalocyaninate [(15C5)₄Pc]In(OH) are studied in detail. Field dependence of the quantum efficiency in a 7.8 μm-thick layer containing 5 at % [(15C5)₄Pc]In(OH) is measured. The best approximation of the quantum efficiency with Onsager’s equation corresponds to a quantum yield of thermalized electron-hole pairs φ₀ = 0.01 at initial separation r ₀ = 9.8 Å. Z-scan measurements in a nanosecond range showed that the electric susceptibility of [(15C5)₄Pc]In(OH) solution in tetrachloroethane (TCE) with a concentration of 7 × 10^?4 mol/L is χ⁽³⁾ = 1.34 × 10^?9 esu. The maximum coupling gain coefficient found for the material composed of PVK and 5 wt % [(15C5)₄Pc]In(OH) at an electric-field intensity of 200 V/μm is Γ = 80 cm^?1, and the difference between the coupling gain and absorption coefficients is Γ ? α = 70 cm^?1. The dependence of the coupling gain coefficient on the intensity ratio of interfering beams 1 and 2 (β = I ₁(0)/I ₂(0)) in a composite containing 3 wt % [(15C5)₄Pc]In(OH) is measured. An increase in β was attained by decreasing intensity of the signal beam I ₂(0) at constant intensity of the pump beam I ₁(0) = 0.15 W/cm² and E ₀ = 214 V/μm. Within the initial segment of the curve, the coupling gain coefficient increases from 30 to 60 cm^?1; then, the coefficient drops almost to the initial value. The data obtained show that the composite materials studied can be used in practice for correcting faded images. The combined analysis of the results obtained and similar data for gallium and ruthenium tetra-15-crown-5-phthalocyaninate complexes revealed the regularities in the change of the quantum yield of thermalized electron-hole pairs and the photorefractive coupling gain coefficient in a series of complexing metals: gallium(III), ruthenium(II), and indium(III). An increase in the molecular weight of the central metal atom is found to result in a substantial decrease in Γ and φ₀ due to the increase in the spin-orbit coupling constant.     

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.     

Potassium-promoted anionic selectivity of lanthanide bis(tetra-15-crown-phthalocyaninate) complexes

The interaction between neutral, lanthanide bis(tetra-15-crown-5-phthalocyaninate) complexes Ln[(15C5)₄Pc]₂⁰, (Ln = La, Tb, and Tm) and potassium bromide, picrate, or tetraphenylborate in chloro-form-acetonitrile solutions is studied using the spectrophotometric titration. The architecture of the supramolecular aggregates formed is shown to depend on the size of the lanthanide ion introduced into crown-phthalocyaninate and the nature of potassium salt anion.     

Magnesium Octa[(4'-Benzo-15-Crown-5)-Oxy]Phthalocyaninate in Low-Molecular Hydrogels: Spectral Properties and Release under Stimulation

This work is dedicated to low-molecular hydrogels based on biodegradable sodium deoxycholate (SDC) and lysine hydrochloride (lys × HCl) with magnesium octa-[(4'-benzo-15-crown-5)-oxy]phthalocyaninate (Mgcr₈Pc) as the active component, namely, their synthesis, spectral properties of gel-solubilized Mgcr₈Pc, its release from the gel etc. Addition of Mgcr₈Pc occurs both via the mixing of the components and via its diffusion from the aqueous solution into the phase of the formed SDC/lys × HCl gel. Mgcr₈Pc-containing hydrogels are thermoreversible. The state of Mgcr₈Pc in the SDC/lys × HCl/NaCl gel at the room temperature and in the melt is studied using spectral methods. Gel melting releases Mgcr₈Pc in the form of a micelle-bound monomer. The presence of the Mgcr₈Pc monomer phase in the phthalocyanine-carrying supramolecular hydrogel causes fluorescent activity of the latter.     

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.     

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.     

The effect of aggregate state of octa-(benzo-15-crown-5)-substituted phthalocyanines in aqueous solutions on the structure of self-organized composites of ultrathin ion layers

The method of layer-by-layer (LbL) deposition from aqueous solutions was used to obtain electrostatic self–organized composites consisting of cationic fragments of octa-[(4′-benzo-15-crown-5)oxy]phthalocyaninates of metals (Mcr8Pc)/K⁺ and anionic fragments of sodium polystyrenesulfonate or 4,4′,4″,4?-[cobalt phthalocyaninate-2,(3),9,(10),16,(17),23,(24)-tetrayl-tetrakis(oxy)]-tetrabenzoic acid. The electronic absorption spectra of composite coatings indicate preservation of structures formed in aqueous solutions of Mcr₈Pc: coaxial associates, noncoaxial associates, and high-order aggregates. An increase in the content of noncoaxial associates and the possible presence of suspension particles in the composite are observed.     

Bridged polysilsequioxane adsorption materials containing phosphonic acid residues

Reactions of hydrolytic polycondensation of bis(triethoxysilane) [(C₂H₅O)₃Si]₂C₂H₄ (or [(C₂H₅O)₃Si]₂C₆H₄) and functional agent (C₂H₅O)₃Si(CH₂)₂P(O)(OC₂H₅)₂ (alkoxysilanes molar ratio of 2: 1 and 4: 1, fluoride ion catalyst and ethanol solvent) yielded powder-like xerogels that contained phosphonic acid residues in the surface layer. Their treatment with boiling concentrated hydrochloric acid resulted in transformation of functional groups ≡Si(CH₂)₂P(O)(OC₂H₅)₂ into acid groups ≡Si(CH₂)₂P(O)(OH)₂. The methods of IR, ¹H MAS NMRm and ¹³C, ²⁹Si, ³¹P MAS NMR spectroscopy showed the following (1) The surface layer in the initial xerogels contains not only phosphorus functional groups, but also some non-hydrolyzed ethoxysilyl groups as well as silanol groups. (2) The hydrochloric acid treatment of the initial xerogels causes the hydrolysis of not only ethoxy groups in the phosphonic acid residues, but also most residual ethoxysilyl groups. (3) Vacuum drying of xerogels after acid treatment forms ≡Si(CH₂)₂P(O)(OH)-OSi≡ links in their surface layer (not more than 20% of phosphorus-containing groups). (4) According to ²⁹Si CP MAS NMR spectroscopic data, boiling acid treatment relatively enriches the xerogel structure T² and T³ units and accounts for the higher rigidity of the hybrid framework. These units also account for retention of the porous structure in these xerogels over time, while most initial xerogels have porous structures that collapse in 12–18 months of storage. The acid-treated xerogels were attributed to microporous adsorbents (having specific surface area of 620 to 760 m²/g). According to the AFM data, both initial and acid-treated xerogels contain almost spherical aggregates of the primary particles (globules).     

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.     

Lanthanide complexes with acetylacetonate and 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin

Lanthanide complexes of acetylacetonate and 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin having the general formula Ln[(FBOEP)₄P]acac (where Ln=Ho, Er, Yb, Lu; FBOEP=[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenyl; Hacac=acetylacetone; P=porphyrin) have been prepared and characterized. A structure is proposed in which one 5,10,15,20-tetra[para-(4-flourobenzoyloxy)-meta-ethyloxy]phenylporphyrin is coordinated to a rare earth ion in a tetradentate fashion, while one acetylacetonate is coordinated to the same metal ion in a bidentate fashion. We investigated the photo-generated charge behavior of the ligand and the complex, Lu[(FBOEP)₄P]acac, by means of surface photo-voltage spectroscopy (SPS) and field induced surface photo-voltage spectroscopy (FISPS) which are useful tools to investigate the photo-physics of excited states generated by absorption in the aggregate state.     

A paddlewheel dinuclear Cu(II) compound coordinated with TTF-py redox ligand

A new paddlewheel dinuclear complex with a pyridyl-tetrathiafulvalene (TTF-py) ligand has been obtained and characterized crystallographically as [(DMT-TTF-py)₂Cu₂(OAc)₄]·2C₆H₆ (1). Meanwhile a mononuclear compound [(DMT-TTF-py)₂Cu(PhCOO)₂(CH₃OH)₂]·2CH₂Cl₂ (2) was also isolated. UV–vis spectra and cyclic voltammogram of the paddlewheel complex were studied, showing that compound 1 can undergo an oxidization to form a stable cation of [(DMT-TTF-py)₂Cu₂(OAc)₄]²⁺. By this strategy, compound 3, [(DMT-TTF-py)₂Cu₂(OAc)₄](I₃)₂ as a radical salt, has been prepared and its conductivity of powder sample was 1.02 × 10^?3 ohm^?1 cm^?1. Antiferromagnetic coupling of Cu(II)–Cu(II) was found from the results of ESR spectra, but the coupling between the radical–Cu(II) was very weak.     

Fluorescence and preparation of Sr2（P2O7）：Ce,Tb phosphate by co-precipitation method

The micron-sized Sr2（P2OT）：Ce,Tb green phosphors were prepared by being annealed at different temperatures with its precursors synthesized by co-pre-cipitates of （NH4）2HPO4 at ambient temperature. The phase structure, grain size, surface morphology, and luminescent properties of phosphors were investigated by X-ray diffraction, scanning electron microscope, trans-mission electron microscope, and fluorescence spectrum. The results show that the product of precursor annealed at 1,100 ℃ is Sr2（P2O7）：Ce,Tb, which belongs to ortho-rhombic phase. The powder is spherical and the size dis-tribution is in micron grade. The sample with the molar ratio of Sr/Tb/Ce of 100.0：0.4：0.6 shows the best fluores-cence effect annealed at 1,100 ℃ for 3 h. The phosphors produce green fluorescence by being excitated with ultra-violet radiation of 254 nm wavelength, and the main emission peak is at 547 nm. The Sr2（P2O7）：Ce,Tb phos-phors synthesized by co-precipitation method of precursors at ambient temperature is a kind of efficient green-emitting phosphors.     

One-step chemical synthesis of doped polythiophene by use of copper(II) perchlorate as an oxidant

A reaction of 2,2′-bithiophene with copper(II) perchlorate in acetonitrile achieved polymerization and doping in one step, and yielded polythiophenes, [(C₄H₂S)(ClO₄)_x·yH₂O]_n. The polymers with x ∼ 0.17 and y ∼ 0.3 exhibited a high electrical conductivity in the range 3 – 8 S cm⁻¹ at 300 K and a small activation energy of 0.04 eV. The i.r. and e.s.r. spectra showed the characteristics of doped polythiophenes.     

Perdeuterio bis(ethylenedithio)tetrathiafulvalene

The deuterated S-based organic donor molecule bis(ethylenedithio)-tetrathiafulvalene 5b, C₁₀S₈D₈, was synthesized with high deuterium purity (99.7+%) by phosphite coupling of the thione intermediate perdeuterio-4,5-ethylenedithio-1,3-dithiole-2-thione 3b, C₅S₅D₄, or the carbonyl intermediate perdeuterio-2,5,7,9-tetrathiabicyclo [4.3.0] non-1(6)-en-8-on 4b, C₅S₄-OD₄. 3b was prepared by the addition of D₄-ethylenedibromide to an alcoholic solution of 1,3-dithole-2-thione-4,5-dithiolate that was generated by the reaction of sodium with carbon disulfide in N,N-dimethylformamide. No deuterium exchange with solvents during the course of reactions was observed. Compounds 3b-5b, and their isotopic purity, were established by use of mass, NMR, FT-IR and UV-visible spectrometry.     

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.     

Stability of tungsten oxide nanotubes film for improving photocatalytic oxidation reaction

Well-aligned anodic tungsten oxide (WO₃) nanotubes with lengths approaching 600 nm was successfully synthesised via electrochemical anodisation of tungsten (W) film at 40 V in a bath with electrolyte (pH 3) consisted of 1 M of sodium sulphate (Na₂SO₄) and 0.7 wt-% ammonium fluoride (NH₄F) for 15 min. It was found that the production of dense compact oxide layer on pure W film could be explained with high concentration of H⁺ ions accelerated the hydrolysis ability on the W surface to form thick WO₃ layer under acidic condition (pH: 3). The photocatalytic activity performance was increased by ≈15% for the dense WO₃ nanostructures film as compared to the thin and irregular WO₃ nanostructures film because of the high active surface area to absorb more photons from solar irradiation for triggering the charge carriers separation and then improvement of internal and external diffusion of the reactants.     

Preparation and characterization of a layered perovskite-type organic–inorganic hybrid compound based on (C6H4)2N (CH2)6NH3Cl

The organic–inorganic hybrid compound ((C₆H₄)₂N(CH₂)₆NH₃)₂PbCl₄ (N6AHMC–PbCl₄) and ((C₆H₄)₂N(CH₂)₆NH₃)₂PbCl₂I₂ (N6AHMC–PbCl₂I₂) were synthesized by treating N-6-aminohexamethylcarbazole chloride (N6AHMC–HCl) with stoichiometric amount of PbX₂ (X = Cl, I) at room temperature using dimethylformamide (DMF) as solution. High order diffraction peaks corresponding to (0 0 l) (l = 2, 4, 6, …) were observed in the X-ray diffraction profile of N6AHMC–PbCl₄ and N6AHMC–PbCl₂I₂, indicating the formation of hybrid crystal with layered perovskite structure. N6AHMC–PbCl₄ presented characteristic absorptions of PbCl-based layered perovskite centered at about 329 nm. Similar to the PL spectrum of N6AHMC–HCl, the film of N6AHMC–PbCl₄ showed three strong emission peaks, indicating that the exciton emission of the N6AHMC–PbCl₄ film comes from the organic layer of the hybrids. Owing to the partially replacement of Cl^? with I^?, the fluorescence quenched N6AHMC–PbCl₂I₂ showed broad absorption at about 400 nm, which is assigned to the transition from the hybrid orbital hybridized by Cl 3p and I 5p valence states to Pb 6p conduction bands. For the reason of the variation of the energy band structure, from type I quantum well structure to type II heterojunction, the photoconductivity of N6AHMC–PbCl₂I₂ is higher than that of N6AHMC–PbCl₄.