- Facile one-pot preparation of thermally and photochemically convertible soluble precursors of copper phthalocyanine and naphthalocyanine
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Soluble copper phthalocyanine (CuPc) and naphthalocyanine (CuNc) precursors which can be converted thermally and photochemically into insoluble CuPc and CuNc, respectively, have been synthesized by a one-step reaction using commercially available chemicals. The Royal Society of Chemistry 2011.
- Kikukawa, Yuu,Fukuda, Takamitsu,Fuyuhiro, Akira,Ishikawa, Naoto,Kobayashi, Nagao
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- Effect of chain length on thermal conversion of alkoxy-substituted copper phthalocyanine precursors
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A series of dialkoxy-substituted copper phthalocyanine (CuPc) precursors (4a-4d) have been prepared by treating phthalonitrile with the corresponding lithium alkoxide under mild conditions. The precursors exhibited high solubilities in common organic solvents, including acetone, toluene, tetrahydrofuran (THF), CH2Cl2, and CHCl3. Elongation of the alkoxy chains improved the solubilities of the precursors effectively, and accordingly, the butoxy-substituted derivative (4d) showed the highest solubility among 4a-4d. X-ray crystallography clarified that the conjugated skeletons of 4a-4d are all isostructural, and have two alkoxy groups in a syn-conformation fashion, leading to highly bent structures. Thermal conversions of the precursors examined by thermogravimetry (TG) and differential thermal analysis (DTA) demonstrate that 4a was converted into CuPc via two distinct exothermic processes in the 200-250 °C temperature range, while 4d exhibits only one exothermic signal in the DTA. In the field emission scanning electron microscopy (FESEM) images of 4a, the presence of two types of distinct crystal morphology (prismatic and plate-like crystals) can be recognized, implying that the two observed exothermic processes in the DTA can be attributed to the different crystal morphologies of the samples rather than the step-by-step elimination of the alkoxy groups. The thermal formation of CuPc from the precursors has been unambiguously confirmed by X-ray powder diffraction, UV-vis spectroscopy, and elemental analysis. The precursors were converted into CuPc at lower temperature with increasing chain length, presumably because of the increased void volume in the crystals. Thermal conversion performed in the solution phase results in a bright blue-colored solution with prominent absorption bands in the 650-700 nm region, strongly supporting the formation of CuPc.
- Fukuda, Takamitsu,Kikukawa, Yuu,Tsuruya, Ryota,Fuyuhiro, Akira,Ishikawa, Naoto,Kobayashi, Nagao
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- (Phthalocyaninato)copper(II) complexes fused with different numbers of 15-crown-5 moieties - Synthesis, spectroscopy, supramolecular structures, and the effects of substituent number and molecular symmetry
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Symmetrical (phthalocyaninato)copper(II) complexes Cu(Pc′) [Pc′ = Pc(15C5), Pc(opp-15C5)2, Pc(adj-15C5)2, Pc(15C5) 3; Pc = unsubstituted phthalocyaninate, Pc(15C5) = 2,3-(15-crown-5)phthalocyaninate, Pc(opp-15C5)2 = 2,3,16,17-bis(15-crown-5)phthalocyaninate, Pc(adj-15C5)2 = 2,3,9,10-bis(15-crown-5)phthalocyaninate, Pc(15C5)3 = 2,3,9,10,16,17-tris(15-crown-5)phthalocyaninate] (2-5) have been prepared by the reaction of corresponding heteroleptic bis(phthalocyaninato)europium complexes Eu(Pc)(Pc′) [Pc′ = Pc(15C5), Pc(opp-15C5)2, Pc(adj-15C5)2, Pc(15C5)3, Pc(15C5)4; Pc = unsubstituted phthalocyaninate] with Cu(OAc)2 in dry dmf at 100°C. For the purpose of comparative studies, the symmetrical counterparts CuPc (1) and CuPc(15C5)4 [Pc(15C5)4 = 2,3,9,10,16,17,24, 25-tetrakis(15-crown-5)phthalocyaninate] (7) have also been prepared. These monomeric complexes have been characterized by spectroscopic methods in addition to elemental analysis. Having a series of closely related phthalocyanines with a different number and/or disposition of 15-crown-5 groups at the peripheral positions, the effects of 15-crown-5 substituent number and molecular symmetry on the electronic absorption spectra, infra-red (IR) spectra, and supramolecular structure formation induced by K+ ions have been investigated. Systematic studies on the formation of dimeric supramolecular structures of the series of monomers 2-6 reveal and confirm the previously proposed two-step three-stage process of K+-induced dimerization of phthalocyanines with three or four 15-crown-5 moieties. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Sheng, Ning,Zhang, Yuexing,Xu, Hui,Bao, Meng,Sun, Xuan,Jiang, Jianzhuang
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- A Bipolar and Self-Polymerized Phthalocyanine Complex for Fast and Tunable Energy Storage in Dual-Ion Batteries
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Bipolar redox organics have attracted interest as electrode materials for energy storage owing to their flexibility, sustainability and environmental friendliness. However, an understanding of their application in all-organic batteries, let alone dual-ion batteries (DIBs), is in its infancy. Herein, we propose a strategy to screen a variety of phthalocyanine-based bipolar organics. The self-polymerizable bipolar Cu tetraaminephthalocyanine (CuTAPc) shows multifunctional applications in various energy storage systems, including lithium-based DIBs using CuTAPc as the cathode material, graphite-based DIBs using CuTAPc as the anode material and symmetric DIBs using CuTAPc as both the cathode and anode materials. Notably, in lithium-based DIBs, the use of CuTAPc as the cathode material results in a high discharge capacity of 236 mAh g?1 at 50 mA g?1 and a high reversible capacity of 74.3 mAh g?1 after 4000 cycles at 4 A g?1. Most importantly, a high energy density of 239 Wh kg?1 and power density of 11.5 kW kg?1 can be obtained in all-organic symmetric DIBs.
- Wang, Heng-guo,Wang, Haidong,Si, Zhenjun,Li, Qiang,Wu, Qiong,Shao, Qi,Wu, Lanlan,Liu, Yu,Wang, Yinghui,Song, Shuyan,Zhang, Hongjie
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- Magneto-modified catalyst on the base of nanocrystalline CuO
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The weakly oxidized nanocrystalline copper powders of different sizes (average particle size of 30 and 100nm) were used as the reactants at copper phthalocyanine (PcCu) formation. The nanocrystalline cupric oxide located at the particles surface serves as a heterogeneous magneto-controlled catalyst. A new effect of acceleration of chemical reaction rate controlled by low external steady magnetic field (～2 kOe) at room temperature was revealed and investigated on an example of formation of a coordination compound of PcCu. The rate of PcCu formation accelerated by 7-8 times after applying of a magnetic field.
- Yermakov,Feduschak,Sedoi,Uimin,Mysik
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- X-ray analysis of phthalocyanines formed in the reaction of Au-Cu and Au-Sn alloys with 1,2-dicyanobenzene
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X-ray investigations of the reactions of copper, tin and their alloys with gold, with 1,2-dicyanobenzene at 210°C have been performed. It was found that under the conditions used, gold does not take part in the reaction with 1,2-dicyanobenzene, but separates from the alloys. Copper and tin phthalocyanines are formed as the main products of the above reactions. The crystal structure of tin phthalocyanine (SnPC) has been determined. SnPc crystallizes in the triclinic system (a = 12.048(3) A, b = 12.630(3) A, c = 8.671(3) A, α = 95.85(5)°, β = 95.10(5)°, γ = 68.25(5)°), space group P1, Z = 2. The refined structure with anisotropic temperature factors have R = 0.041. The Sn atom is coordinated by four isoindole N atoms, the average Sn-N distance being 2.267(6) A. The SnPc molecule is not planar. The Sn atom is 1.1286 A out of the plane of the four coordinating N atoms.
- Kubiak, Ryszard,Janczak, Jan
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- Synthesis and characterization of copper phthalocyanine and tetracarboxamide copper phthalocyanine deposited mica-titania pigments
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Combination pigments were synthesized by the deposition of copper phthalocyanine and tetracarboxamide copper phthalocyanine on a mica-titania pigment in dimethyl formamide solvent to improve color properties. The FT-IR and XRD analyses were performed to observe the crystal transformations of the pigments on the substrate. The stable beta form of copper phthalocyanine normally preferred in paint applications was obtained at 90 °C and 120°C, while tetracarboxamide copper phthalocyanine remained amorphous at all temperatures experimented. Pigment surface morphologies were investigated by SEM analysis. Copper phthalocyanine crystalline rods were observed on the mica-titania substrate, however, the tetracarboxamide copper phthalocyanine pigment did not exhibit any such crystalline structure due to its amorphous structure, which was confirmed by XRD analysis. Furthermore, nitrogen elemental analysis was performed to determine the amount of copper phthalocyanines adsorbed to the mica-titania surfaces at different temperatures. The resulting combination pigments showed enhanced luster, good dispersion, hue, and high color intensity.
- Topuz, Berna Burcu,Guenduez, Guengoer,Mavis, Bora,Colak, Uener
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- Facile, liquid phase preparation of copper phthalocyanine microcrystals by means of thermal conversion of the dimethoxy-substituted solvent soluble phthalocyanine precursors
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A simple procedure for the preparation of microcrystals of insoluble copper phthalocyanine (CuPc) by thermolysis of a dimethoxy-substituted precursor has been developed. Although the morphologies of the resultant microcrystals are practically independent from initial solution concentrations higher than ca. 0.03 mM of the dimethoxy-precursor, crystals with increased width are obtained with increasing the initial concentration of the precursor.
- Fukuda, Takamitsu,Ishikawa, Naoto
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- Improvement in the synthesis of metallophthalocyanines using microwave irradiation
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A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure. Graphical Abstract.
- Burczyk, Aleksandra,Loupy, André,Bogdal, Dariusz,Petit, Alain
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- SYNTHESIS OF PHTHALOCYANINES FROM PHTHALONITRILE WITH ORGANIC STRONG BASES
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In the presence of 1,8-diazabicycloundec-7-ene or 1,5-diazabicyclonon-5-ene, metal-free phthalocyanine was obtained by heating phthalonitrile in alcohols.Addition of a copper(II) salt in the reaction gave copper phthalocyanine in a good yield.
- Tomoda, Haruhiko,Saito, Shojiro,Ogawa, Shojiro,Shiraishi, Shinsaku
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- Femtosecond nonlinear optical response of metallophthalocyanine films
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The third-order nonlinear optical properties of copper phthalocyanine (CuPc) and magnesium phthalocyanine (MgPc) films were investigated by femtosecond optical Kerr effect (OKE) and pump-probe techniques. For both CuPc and MgPc, the third-order nonlinear optical susceptibility was enhanced at least by one order of magnitude in comparison with that of the metal-free Pc, and the enhancement effect arises from different mechanisms for both films. From pump-probe measurement, quite different transmittance and decay behavior between CuPc and MgPc films were observed. The CuPc films show an ultrafast decay, while the decay behavior of MgPc film is complicated with several temporal components, which could be explained by the relaxation of singlet excited state.
- Ma, Guohong,Guo, Lijun,Mi, Jun,Liu, Ye,Qian, Shixiong,Pan, Daocheng,Huang, Yue
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- Studies on polymorphic modifications of copper phthalocyanine
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Four α-, β-, γ- and ε-polymorphic forms of copper phthalocyanine are synthesized. They are characterized and their properties are compared based on the IR spectral measurements in the finger print region, magnetic susceptibility measurements, ESR study, p
- Achar,Lokesh
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- Effects of MN4-Type Coordination Structure in Metallophthalocyanine for Bio-Inspired Oxidative Desulfurization Performance
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Oxidative desulfurization (ODS) is the promising new method for super deep desulfurization of fuel oil. The oxidative desulfurization performance of the metal-N4-chelates metallophthalocyanines (MPcs) is related to the chemical properties of conjugate structures and the central metal ions. Herein, a biomimetic catalytic system composed of metallophthalocyanines (MPcR4, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II); R = -H, -COOH, -NO2, -NH2) and molecular O2 was performed to study the influence of MN4-type coordination structure in metallophthalocyanines for the degradation of dibenzothiophene (DBT) in model oil containing n-octane. The results reveal that the conjugate structures and the center metal ions of metallophthalocyanines played key roles in oxidative desulfurization performance. The inductive effect of different R substituents strongly affected the electron cloud distribution of the conjugate structures and the catalytic performance. Moreover, the catalytic activity of MPcs, which is related to the d electronic configuration and ligand-field effects, does not sequentially increase with the increase in the d electron number of central metal ions.
- Tan, Amin,Tian, Min,Yang, Yan,Zhang, Gai,Zhang, Yufan
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- Sustainable approaches to the synthesis of metallophthalocyanines in solution
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This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.
- Imperatori, Patrizia,Paoletti, Anna Maria,Pennesi, Giovanna,Zanotti, Gloria
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supporting information
(2021/06/15)
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- Nanostructural catalyst: Metallophthalocyanine and carbon nano-onion with enhanced visible-light photocatalytic activity towards organic pollutants
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Metallophthalocyanine (MPc) and carbon nano-onion (CNO) derivatives were synthesized and characterized by using ultraviolet-visible spectroscopy, infrared and Raman spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy and X-ray powder diffraction. The unmodified CNOs and MPc-CNO derivatives were used as photocatalysts for rhodamine B (RhB) degradation under visible-light irradiation. The photocatalytic studies revealed that the MPc-CNO nanostructural materials simultaneously exhibited a high absorption capacity and an excellent visible-light-driven photocatalytic activity towards RhB. These nanostructures possess great potential for use as active photocatalysts for organic pollutant degradation.
- Brzezinski, Krzysztof,Butsyk, Olena,Chaur, Manuel N.,Czyrko-Horczak, Justyna,Echegoyen, Luis,Olejnik, Piotr,Plonska-Brzezinska, Marta E.,Regulska, Elzbieta,Tomczykowa, Monika,Zubyk, Halyna
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p. 10910 - 10920
(2020/03/30)
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- NANOPARTICLE DISPERSION CONTAINING A DYE
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A method for preparing a dispersion of nanoparticles of a solid organic dye or pigment in a liquid carrier, the method comprising continuously mixing: at least one solution or slurry containing a reactant precursor for the solid organic dye or pigment in an organic or other solvent with the liquid carrier in a counter current or concurrent mixing reactor whereby to obtain reaction of the reactant precursor and formation of the solid organic dye or pigment as a dispersion of nanoparticles in the liquid carrier and solvent mixture; optionally, removing unreacted reactant precursor and/or byproduct from the dispersion when present; and optionally, concentrating the dispersion.
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(2019/07/13)
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- A simple synthesis of symmetric phthalocyanines and their respective perfluoro and transition-metal complexes
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We report a simple synthesis protocol for making phthalocyanines (Pcs) starting from phthalonitriles. This method is general and requires no specialised equipment. The complexes are isolated and characterised using X-ray diffraction, NMR, FTIR and Raman spectroscopy and high-resolution mass spectrometry. First, we study and present a one-step synthesis route to a metal-free Pc (H2PcH16), as well as to the corresponding MPcH16 complexes of Mn, Fe, Co, Ni, Cu and Zn. Then, we show that this route can also be used to make the fluorinated Pc analogues (MPcF16). Finally, we present a new and useful procedure for inserting a metal ion into a metal-free H2PcH16 ring, by direct metalation, yielding the corresponding MPcH16 complex. This last method is especially useful if you want to make different MPcH16 complexes.
- Denekamp, Ilse M.,Veenstra, Florentine L.P.,Jungbacker, Peter,Rothenberg, Gadi
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- Copper phthalocyanine as an efficient and reusable heterogeneous catalyst for direct hydroxylation of benzene to phenol under mild conditions
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The liquid-phase oxidation of benzene to phenol over copper phthalocyanine as a heterogeneous catalyst was studied at room temperature. Acetonitrile was chosen as the preferred solvent and hydrogen peroxide as an eco-friendly oxidant. The yield and selectivity of 13.9% and 100% were obtained, respectively. The catalyst was characterized by FT-IR, UV-Vis, XRD, TGA, XPS, 1H NMR, 13C NMR, CHN, BET, FE-SEM, TEM, and EDX analysis. The effects of different parameters on the catalytic performance of CuPc were also investigated. The reusability of the catalyst was studied, and the results showed that after five cycles the yield of phenol did not change noticeably, probably due to its stability in the reaction conditions.
- Farahmand, Shohreh,Ghiaci, Mehran,Razavizadeh, Jala.S.
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p. 174 - 179
(2018/09/29)
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- Method for synthesizing metal phthalocyanine from phthalonitrile under catalysis of urea-choline chloride
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The invention provides a clean method for synthesizing metal phthalocyanine from phthalonitrile or a phthalonitrile derivative substituted by different functional groups and a metal chloride or nitrate under catalysis of a urea-choline chloride eutecticevaporate green solvent. Multiple functional metal phthalocyanine compounds such as cobalt, copper, zinc, nickel, iron and manganese are synthesized under a gentle condition, the yield is high, and in addition, toxic and organic solvents such as amyl alcohol and expensive DBU (diazabicyclo) organic alkali catalysts which are used in a conventional process are not used. The urea-choline chloride eutecticevaporate solvent DES is adopted as a solvent for dissolving and dispersing reactants, meanwhile, a function of catalyzing formation of a phthalocyanine cycle is also achieved, and the reaction temperature for forming the phthalocyanine cycle is 110-130 DEG C. The low reaction temperature also ensures the uniformity, completeness and highpurity of a phthalocyanine product structure. The synthesis process is green, remarkable environment benefits can be made, the energy can be saved, and meanwhile, environment protection can be achieved.
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Paragraph 0013
(2019/11/13)
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- A nitrogen-doped porous carbon derived from copper phthalocyanines on/in ZIF-8 as an efficient photocatalyst for the degradation of dyes and the C[sbnd]H activation of formamides
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A novel nitrogen doped carbon photocatalyst was successfully prepared from the carbonization of copper phthalocyanine (CuPc) on/in zeolitic imidazolate framework-8 (ZIF-8) hybrid. Carbonized catalysts derived from either ZIF-8 or CuPc exhibit poor activity towards the degradation of dyes (such as methyl orange (MO) and Rhodamine B (Rh B)), whereas carbonized CuPc complex supported on ZIF-8 exhibits extremely high performance. The weight ratios 1:2 and 1:8 of CuPc/ZIF-8 showed the high dye absorption activity, while the weight ratio 1:4 demonstrated the high photocatalytic activity in the presence of H2O2 as an oxidant. For the first time, the photocatalyst (Cu/N-PC) was used in C[sbnd]H activation of formamides in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant. The reaction proceeded within 30 min, in the presence 0.02 mol% of Cu.
- Movahed, Siyavash Kazemi,Piraman, Zeinab,Dabiri, Minoo
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p. 208 - 224
(2017/10/31)
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- Nano magnetite supported phthalocyanine complexes of Cu(II) and Fe(II) as new heterogeneous effective catalysts for synthesis of β-amido ketones
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In this study, a novel, heterogeneous and reusable catalyst prepared by the coordinative anchoring of metal(II) phthalocyanine complexes (M: Fe, Cu) on the guanidine-functionalized magnetic nanoparticles was reported. The synthesized catalysts were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermal gravimetric analysis (TGA), and FT-IR measurements. The catalysts were used successfully in the synthesis of β-amido ketones. This method provides several advantages including little catalyst loading, absence of any tedious workup or purification and at least six times reusability of the catalyst without any remarkable change in the catalytic activity. (Figure presented.).
- Naeimi, Hossein,Rahmatinejad, Soraya
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p. 4210 - 4227
(2019/01/19)
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- SYNTHESIS OF COPPER PHTHALOCYANINE USING DEEP EUTECTIC SOLVENT
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The present disclosure generally relates to synthesis of copper phthalocyanine. In particular, the present disclosure relates to a method of synthesis of copper phthalocyanine using deep eutectic solvent (DES), which can be carried out at low temperature, does not involve use of high boiling solvents, uses less urea and allows solvents used in the process to be recycled.
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Paragraph 0049
(2017/11/04)
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- Preparation method for metal phthalocyanine crystal
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The invention discloses a preparation method for a metal phthalocyanine crystal. The preparation method comprises the following steps: successively adding phthalonitrile and a metal copper sheet into a reaction vessel, then adding an anhydrous ethanol solvent, sealing the reaction vessel, carrying out a solvothermal reaction in a baking oven with a temperature of 180 to 200 DEG C for no less than 3 h, stopping heating after completion of the reaction and carrying out natural cooling to room temperature. A suction pipe is used for meticulous suction of the obtained acicular copper phthalocyanine crystal; then the acicular copper phthalocyanine crystal is soaked and flushed with hot ethanol to remove residual reactants adsorbed on the surface of copper phthalocyanine; and drying is carried out, so purification of the acicular copper phthalocyanine crystal is finished. The method can directly prepare the copper phthalocyanine crystal with regular acicular appearance through one-step reaction without recrystallization. The preparation method is simple to operate, green, pollution-free, and free of production of harmful pollutants; moreover, the method uses the copper sheet as a reactant, so complicated post-treatment during purification caused by usage of a copper salt in the prior art is avoided, the purification process is simple and easily practicable and meets practical production needs.
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Paragraph 0023; 0024; 0025; 0026; 0027
(2017/08/27)
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- A method of manufacturing a copper phthalocyanine compound
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PROBLEM TO BE SOLVED: To provide a process for producing a copper phthalocyanine compound capable of preventing blockage of a gas discharge pipe during an imidation reaction by a simple reform of a production apparatus.SOLUTION: The process for producing a copper phthalocyanine compound comprises: (a) allowing phthalic acid and ammonia to react with each other in an organic solvent to obtain phthalimide, discharging gas containing at least the organic solvent and steam as a reaction product from a reaction apparatus, and allowing the reaction to proceed while liquefying the discharged organic solvent gas in the discharge pipe and returning the solvent to the reaction apparatus, as a first step; and (b) allowing the phthalimide obtained in the first step to react with a copper compound and urea in the presence of a catalyst to obtain a copper phthalocyanine compound, as a second step. In the first step, a temperature (T1) of the discharge pipe is set to a temperature satisfying the relation of T2≤T1T3 with respect to the boiling point (T2) and the boiling point (T3) of the organic solvent under the pressure in the first step.
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Paragraph 0036
(2017/04/07)
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- Cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanines covalently supported on wool: Synthesis, characterization and catalytic activity
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Functionalized wool with cobalt(II), copper(II), and iron(II) tetrasulfophthalocyanine (CoTSPc@wool, CuTSPc@wool, and FeTSPc@wool) have been synthesized and their structures characterized by flame atomic absorption spectroscopy (FAAS), FT-IR, UV-vis, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and the energy dispersive spectroscopy (EDS) analysis. The catalytic activity of the synthesized catalysts was investigated for the aerobic oxidation of alkyl arenes and alcohols to their corresponding carbonyl compounds in the absence of any co-promoter and additional oxidizing reagent. We found the best catalyst for the mentioned reactions is the CoTSPc@wool from the solvent, conversion, temperature, and reaction time point of views. The synthesized catalysts can be readily recycled and reused for several runs without significant loss of efficiency.
- Shaabani, Ahmad,Hezarkhani, Zeinab
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p. 677 - 688
(2016/08/30)
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- Systematic study of transition-metal (Fe, Co, Ni, Cu) phthalocyanines as electrocatalysts for oxygen reduction and their evaluation by DFT
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In this work, a facile approach is reported to prepare a series of transition-metal phthalocyanines (TMPc) supported on graphitized carbon black (TMPc/GCB, TM: Fe, Co, Ni and Cu) as oxygen reduction reaction (ORR) electrocatalysts, via π-π interaction self-assembly. Through transmission electron microscopy (TEM), Raman spectroscopy and UV spectroscopy, it was found that TMPc was coated on graphitized carbon black with non-aggregated morphology. The catalytic activity, both in terms of the onset potential (0.98 V to 0.76 V) and half-wave potential (0.90 V to 0.55 V) follows the trend of FePc/GCB > CoPc/GCB > CuPc/GCB > NiPc/GCB. However, the catalytic durability follows the decreasing order of NiPc/GCB > CoPc/GCB > FePc/GCB > CuPc/GCB. To better elucidate the ORR catalytic mechanism for TMPc/GCB, we employed density functional theory (DFT) calculations and drew the following conclusions: (i) the -O2 adsorption is the major step to determine the ORR catalytic activity; (ii) the way O2 is adsorbed on TMPc is the key point affecting the Tafel slope; (iii) the -H2O2 desorption determines the transfer electron number; and (iv) the -OH desorption and the central metal atom removal leads to the damage affecting catalytic durability.
- Zhang, Zhengping,Yang, Shaoxuan,Dou, Meiling,Liu, Haijing,Gu, Lin,Wang, Feng
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p. 67049 - 67056
(2016/08/02)
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- PHTHALOCYANINE DYE USED FOR COLOR FILTER OF LCD
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Aphthalocyanine dye which is suitable for forming a color filter used for a liquid crystal display device, a composition containing an alkaline soluble resin and the phthalocyanine dye, an article having a polymer layer containing the dye and an alkaline soluble resin and a color filter containing the dye are developed.
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Paragraph 0074; 0082
(2015/02/19)
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- ORGANIC COMPOUND, CHARGE-TRANSPORTING MATERIAL, AND ORGANIC ELECTROLUMINESCENT ELEMENT
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There are provided an organic having both excellent hole transporting property and satisfactory electron transporting and showing excellent durability against electric oxidation/reduction and a high triplet excitation level, and a charge transporting material and an organic electroluminescent device each using the organic compound. The organic compound is represented by following Formula (I): wherein Cz 1 and Cz 2 each represent a carbazolyl group; Z represents a direct bond or an arbitrary linkage group enabling the conjugation of nitrogen atoms in the carbazole rings of Cz 1 and Cz 2 with each other; and Q represents a direct bond connecting to "G" in following Formula (II): wherein Ring B 1 represents a six-membered aromatic heterocyclic ring having "n" nitrogen atom(s) as hetero atom(s); "n" represents an integer of from 1 to 3; G represents a direct bond or an arbitrary linkage group connecting to Q when G connects to Q; Gs connect to carbon atoms at the ortho-position and the para-position with respect to nitrogen atom(s) in Ring B 1 ; G represents an aromatic hydrocarbon group when G does not connect to Q; and "m" represents an integer of from 3 to 5.
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- Porphyrine type compound having a metal complex manufacturing method
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[Problem] To provide a clean and efficient method for producing a metal complex of a compound that has a porphyrin skeleton, which does not use an organic solvent at all during the synthesis and is capable of easily separating a metal complex in a solid state from an aqueous solution of a metal salt after the reaction, and which places extremely little burden on the environment. [Solution] The above-described problem is solved by a method for producing a metal complex of a compound that has a porphyrin skeleton, wherein a compound having a porphyrin skeleton and a metal salt are caused to react with each other in water at a reaction temperature of 200-450°C (inclusive). It is preferable that tetraphenylporphyrin and a metal salt are caused to react with each other in water at a reaction temperature of 300-400°C (inclusive).
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Paragraph 0081
(2016/12/26)
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- Convenient and efficient method for the synthesis of phthalocyanines and metallophthalocyanines in task-specific 2-hydroxyethyl ionic liquids
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Tetramerization of substituted phthalonitriles in task-specific 2-hydroxylethyl-based imidazolium and ammonium ionic liquids at 100 °C gave corresponding phthalocyanines in moderate yield. Further the reaction of substituted phthalonitriles in the presence of transition-metal salts in ionic liquids gave the corresponding metallophthalocyanines. The 2-hydroxylethyl ammonium ionic liquids gave better yields of phthalocyanines than 2-hydroxylethyl imidazolium and nonhydroxyl functionalized ionic liquids. The isolation and separations of different phthalocyanines were accomplished by silica-gel column chromatography, and products were characterized by various spectroscopic techniques.
- Yadav, Kumar Karitkey,Poonam,Chauhan, Shive M. S.
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supporting information
p. 2797 - 2807
(2014/10/15)
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- A COST EFFECTIVE, PROCESS OF CONVERTING WASTE AMMONIA AND CARBON DIOXIDE INTO PHTHALOCYANINE COMPOUNDS VIA INTERMEDIATES
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A cost effective, environment friendly and industrially viable process for the preparation of phthalocyanine compounds more particularly copper phthalocyanine, other metal phthalocyanines and metal free phthalocyanine, the process comprising the steps of:scrubbing the waste ammonia and carbondioxide gaseous streams generated during /byphthalic anhydride - urea processin aqueous solution; saturating the aqueous solution to produce ammonia in the range of about 10-35 %; treating the saturated solution with phthalic anhydride and one or more suitable solvents to convert into phthalocyanine intermediates in the presence of one or more suitable catalyst;converting in-situ the phthalocyanine intermediatesto copper phthalocyanine or other metal / metal free phthalocyanine with the help of minimal amount of urea compound and metal salt.
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Paragraph 36-38
(2014/04/04)
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- Production process for colorant, colorant composition, toner, ink for ink jet recording and color filter
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Provided is a production process for a colorant which contains a silicon phthalocyanine compound making it possible to reach a targeted particle diameter even by a conventional dispersing method and which is excellent in performances such as a color reproducibility, a light fastness, an electrostatic property, a transparency and the like, and a colorant composition, a toner, an ink for ink jet recording and a color filter which are excellent in the above performances. The above production process is a production process for a colorant containing a silicon phthalocyanine compound and a copper phthalocyanine compound and is characterized by having a preparing step of reacting raw materials of a silicon compound and phthalocyanine under the presence of a copper salt or the copper phthalocyanine compound described above to prepare the silicon phthalocyanine compound described above.
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Paragraph 0153
(2013/10/21)
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- Controlled microwave-assisted synthesis of metallophthalocyanines
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A controlled microwave-assisted strategy has been elaborated for the fast and efficient synthesis of metallophthalocyanines scaffold. Compared to the conventional protocol, reproducibility of products was achieved, accompanied by significantly high purity and excellent yields
- Seyyedhamzeh, Mozhdeh,Ganji, Nasim,Shaabani, Ahmad
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p. 1110 - 1113
(2013/01/15)
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- Cobalt(II) phthalocyanine-catalyzed highly chemoselective reductive amination of carbonyl compounds in a green solvent
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Cobalt phthalocyanine has been employed for the highly chemoselective reductive amination of aldehydes and ketones in ethanol as a green solvent. A large range of functional groups such as nitro, acid, amide, ester, nitrile, halogen, lactone, methoxy, hydroxy, alkene, N-benzyl, O-benzyl and heterocyclic rings were well tolerated under the present reaction conditions. Copyright
- Kumar, Vishal,Sharma, Upendra,Verma, Praveen K.,Kumar, Neeraj,Singh, Bikram
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supporting information; experimental part
p. 870 - 878
(2012/05/04)
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- Nanosized charge-transfer salts of metal phthalocyanine iodides ([MPc]I) produced by direct reaction of MPc-silica hybrid nanoparticles with iodine
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An efficient preparation of nanosized charge-transfer (CT) salts of metal phthalocyanine iodides has been achieved by direct reaction of metal phthalocyanine-silica hybrid nanoparticles with iodine. The direct reaction was enabled by the enhanced reactivity of the nanoparticles, which possess enlarged surface areas. TEM observation revealed that the [MPc]I salts thus formed separate from the shell layers of the nanoparticles during the reaction to form rod-shaped nanostructures of hundreds of nanometres in length and about 30 nm in diameter.
- Funabiki, Akira,Mochida, Tomoyuki,Hasegawa, Hiroyuki,Ichimura, Kunihiro,Kimura, Seiji
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p. 483 - 488
(2011/04/21)
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- Effect of N atoms in the backbone of metal phthalocyanine derivatives on their catalytic activity to lithium battery
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Metal phthalocyanine (MPc, M = Mn2+, Fe2+, Co2+, Ni2+ and Cu2+), metal tetrapyridinoporphyrazine, and metal tetrapyrazinoporphyrazine are synthesized by microwave reaction and characterized by elemental analyzer, IR spectroscopy and UV-vis spectroscopy. The catalytic activity of MPc derivatives to Li/SOCl2 battery is evaluated by the relative discharge energy of the battery whose electrolyte contains the compounds. The discharge energy of Li/SOCl2 battery catalyzed by MPc is approximately 0-61% higher than that of Li/SOCl2 battery in the absence of compounds, depending on the central metal ion. To the same central metal ion, the discharge energy of Li/SOCl2 battery catalyzed by MTAP is approximately 60% higher than that by MPc. The discharge energy of Li/SOCl2 battery in which SOCl2 contains MPTpz is approximately 17-19% higher than that of the battery in the absence of compounds, and almost independent of central metal ions. It shows a correlation existing between the structure and the catalytic active sites of MPc derivatives. The double active site model is proposed to interpret the results.
- Xu, Zhanwei,Zhang, Guoxiang,Cao, Zeyuan,Zhao, Jianshe,Li, Hejun
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p. 101 - 105
(2010/06/16)
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- PIGMENT COMPOSITION FOR PRINTING INK, METHOD FOR PRODUCTION THEREOF, AND METHOD FOR PRODUCTION OF PRINTING INK
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The present invention provides a method for producing a pigment composition for a printing ink, which involves the step of dry-milling crude copper phthalocyanine using calcium carbonate having a specific property; a pigment composition for a printing ink; and a method for producing a printing ink using the pigment composition. Specifically, the present invention provides a method for producing a pigment composition for a printing ink, which involves the step of dry-milling crude copper phthalocyanine and calcium carbonate having a primary particle diameter of 20 to 1500 nm in the absence of a resin for a printing ink; a pigment composition produced by the method; and a method for producing a printing ink, which includes the steps of heating a mixture of a pigment composition, a resin for a printing ink and a solvent for the printing ink, and wet-milling the heated mixture.
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Page/Page column 11
(2010/12/17)
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- Highly chemo- and regioselective reduction of aromatic nitro compounds catalyzed by recyclable copper(II) as well as cobalt(II) phthalocyanines
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Copper/cobalt phthalocyanines were established for the first time as catalysts for the very efficient chemo- and regioselective reduction of aromatic nitro compounds to generate the corresponding amines. The selective reduction of nitro compounds was observed in the presence of a large range of functional groups such as aldehyde, keto, acid, amide, ester, halogen, lactone, nitrile and heterocyclic functional groups. Furthermore, the present method was found to be highly regioselective towards the reduction of aromatic dinitro compounds in a short time with high yields. In most of the cases the conversion and selectivity were >99% as monitored by GC-MS. The reduction mechanism was elucidated by UV-vis and electrospray ionization quadrupole time-of-flight tandem mass spectrometry.
- Sharma, Upendra,Kumar, Praveen,Kumar, Neeraj,Kumar, Vishal,Singh, Bikram
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supporting information; experimental part
p. 1834 - 1840
(2010/10/21)
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- PROCESSES FOR THE PREPARATION OF THE ALPHA CRYSTAL POLYMORPH OF METAL PHTHALOCYANINES
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Methods for producing a stabilised alpha copper phthalocyanine are described. More specifically such methods comprise forming a mixture of (a) a compound of the general formula (II), in which, R1 and R2 are independently -CN or -C(O)OH, or R1 and R2 together are -C(O)OC(O)-, -C(O)NHC(O)- or -C(NH)NH(NH)C-, and form a fused five-membered ring structure and R3, R4, R5 or R6 which may be the same or different are -H, a halide, an C1- C5 alkyl, or a substituent group containing a heteroatom; and (b) a tethered compound of the general formula (III), wherein, any adjacent two of R7, R8 and R9 and any adjacent two of R12, R13 and R14 are independently -CN or -C(O)OH, and any of R7, R8, R9, R12, R13 and R14 which are not -CN or - C(O)OH, are -H, a halide, a C1 - C5 alkyl or a substituent group containing a heteroatom, or any adjacent two of R7, R8 and R9 and any adjacent two of R12, R13 and R14 are either -C(O)OC(O)-, -C(O)NHC(O)- or -C(NH)NH(NH)C-, and form a fused five-membered ring structure, the ring structures being the same or different and any R substituents that are not part of the ring structure are -H, a halide, a C1 - C5 alkyl or a substituent group containing a heteroatom; and X is a chain having a backbone of up to two substituted or unsubstituted atoms and the chain comprises an alkane, an alkene or an alkenyl group or a group containing at least one heteroatom; and reacting the mixture with a source of copper in the +I or +II oxidation state to form copper phthalocyanine in predominantly the alpha crystalline form.
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Page/Page column 23-24
(2009/04/25)
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- Method of producing fine particles of metal complex pigment and dispersion containing fine particles of metal complex pigment obtained by the method
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A method of producing fine particles of metal complex pigment, containing the step of reacting a solution of an alkali metal salt of a ligand that constitutes the metal complex with a solution of salts of a metal that constitutes the metal complex, in the course of a laminar flow in a channel; and a method of producing fine particles of metal complex pigment, containing the step of bringing a solution of an alkali metal salt of a ligand that constitutes the metal complex and a solution of salts of a metal that constitutes the metal complex into contact with each other in a channel having an equivalent diameter of 1 mm or less to form a liquid flow.
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Page/Page column 19-20
(2009/09/05)
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- METHOD FOR PRODUCING A PIGMENT
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Provided is a method for producing a pigment, in particular, a metal phthalocyanine, in high yield and in a green process. The method has (1) a step of obtaining a solution mixture by mixing at least one type of compound serving as a raw material for a pigment with a solvent, and (2) a step of obtaining the pigment by reacting the compound while holding the solution mixture at not less than a temperature where a subcritical state or a supercritical state of the solvent occurs.
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Page/Page column 7
(2008/12/07)
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- Efficient synthesis of transition-metal phthalocyanines in functional ionic liquids
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The synthesis of transition-metal phthalocyanines by the reaction of substituted and unsubstituted phthalonitriles in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and metal salts in functional imidazolium, pyridinium and ammonium ionic liquids at 100-140°C, is reported. The best yields of metallated phthalocyanines were achieved in butyl(2-hydroxyethyl)dimethylammonium bromide ionic liquid. Metallation of free-base phthalocyanines with different metal salts in the above ionic liquid has also been achieved in good yields. Georg Thieme Verlag Stuttgart.
- Chauhan,Kumari, Pratibha,Agarwal, Shweta
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p. 3713 - 3721
(2008/09/19)
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- Sulphonated phthalocyanines as effective oxidation photocatalysts for visible and UV light regions
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Attention was paid to the synthesis, chemical modification (sulphonation), characterisation and practical catalytic utilisation of metal free phthalocyanine and a series of phthalocyanines (PHCs) with Zn, Al, Si, Co, Ni, Cu and Ti central atoms. These organometallic compounds are referred to as highly active species due to their ability to produce singlet oxygen upon energy absorption. Photocatalytic efficiency of the prepared PHCs was tested in a model oxidation of 4-chlorophenol under illumination with visible and UV light in agreement with location of their distinctive absorption bands in both these regions. It was shown that different types of phthalocyanines revealed very different photocatalytic activities and only those with a long life-time of the excited triplet states (ZnPHC, SiPHC, AlPHC) effectively interacted with molecular oxygen to form the reactive singlet oxygen. The indispensable role of constant pH (～10) was also clarified in separate experiments. Determined values of quantum yields for reactions carried out in the UV region were always higher than for reactions induced by the visible light.
- Kluson,Drobek,Strasak,Krysa,Karaskova,Rakusan
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p. 213 - 219
(2008/10/09)
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- Low-temperature synthesis of phthalocyanine and its metal complexes
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Conditions for synthesizing unsubstituted phthalocyanine and its metal complexes from phthalonitrile at low temperatures (0-50°C) are optimized. Phthalocyanine and phthalocyaninates are produced under these conditions using activated Rieke metals, metals on inert substrate, sources of soluble metals in the form of unstable metal complexes, zeolites, solid-phase electrosynthesis of phthalonitrile, and UV irradiation. The use of pyrophoric metals is found to be the most efficient due to a large number of defects in their structure favoring the initial stage of phthalonitrile cyclization on a metal matrix. The suggested mechanism of formation of phthalocyanine macrocycle assumes participation of metal agglomerates occurring in activated metals. Pleiades Publishing, Inc., 2006.
- Kharisov,Ortiz Mendez,Rivera De La Rosa
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p. 617 - 631
(2008/10/09)
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- Method of producing a metal phthalocyanine pigment
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A method of producing a metal phthalocyanine pigment, which contains the step of: allowing an alkali metal salt of phthalocyanine to react with a metal salt, in a solvent which is mainly composed of a sulfur-containing aprotic polar solvent.
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Page/Page column 7
(2008/06/13)
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- COMPOUND, CHARGE TRANSPORT MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE
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An object of the invention is to provide a charge transporting material having an excellent heat resistance, excellent filming properties, an excellent charge transporting ability, and excellent light-emitting characteristics and, also, to provide an organic electroluminescent element providing a high luminance and a highly luminous efficiency and having a long life. The invention relates to a charge transporting material comprising a compound having within the molecule two or more pyridine rings substituted at 2-, 4- and 6-positions thereof, which rings do not substantially conjugate each other (provided that the 3- and 5-positions of the pyridine rings may be substituted) and an organic electroluminescent element using the charge transporting material.
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- Improved performance of organic light-emitting diodes using a metal-phthalocyanine hole-injection layer
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In this paper, we systematically investigated the physical characteristics of the various metal phthalocyanines (MPcs) and the influence of the MPcs hole-injection layer on the electroluminescence performance of indium tin oxide/MPc/naphthylphenylbiphenyl diamine (NPB)/ Al q3 LiFAl devices. The characteristics were measured at room temperature with a thickness variation of the MPc layer. The individual highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies of MPcs were derived from the photoelectron emission and the optical absorption measurements. The results showed that the HOMO and LUMO level energies of MPcs are dependent on their central metal atoms. The turn-on voltage for the devices is lowered by inserting MPc layers and remains virtually the same as the MPc layer thickness is adjusted in the range of 5-15 nm. In addition, the turn-on voltage decreases significantly with the increase of the HOMO levels of the MPc films, demonstrating that the MPc/NPB interface instead of the ITO/MPc interface plays an important role in the hole injection.
- Kao, Po-Ching,Chu, Sheng-Yuan,Liu, Shyh-Jiun,You, Zong-Xian,Chuang, Chan-An
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p. H122-H126
(2008/10/09)
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- Use of elemental metals in different grade of activation for phthalocyanine preparation
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Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Special attention is paid to phthalocyanine formation at relatively low temperatures (0-50°C). In case of use of various forms of activated and non-active nickel, it is shown that its most active form causes rapid PcNi formation at 0-25°C without addition of CH 3ONa.
- Kharisov,Coronado, C.E. Cantú,Cerda, K.P. Coronado,Méndez, U. Ortiz,Guzmán, J.A. Jacobo,Patlán, L.A. Ramírez
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p. 1269 - 1272
(2008/10/09)
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- PROCESS AND APPARATUS FOR PREPARING METAL OR NONMETAL PHTHALOCYANINE
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Disclosed herein is a process for preparing a metal or nonmetal phthalocyanine by using both microwave and ultrasonic wave energy in the presence of a solvent, or by using microwave energy in the absence of a solvent. Specifically, according to the process, anhydrous phthalic acid, phthalimide, 1,3-diiminoisoindoline, 1,2-dicyanobenzene, an halogen derivative thereof, an alkyl_ derivative thereof or an alkoxy derivative thereof is mixed with a metal chloride or an alkoxy metal at 130250°C for 0.2515 hours by using microwave at a frequency of 0.1-1000Hz and a power of 100-3,000W and ultrasonic wave at a frequency of 1-1,000GHz and a power of 100-5,000W in the presence of a solvent, or by using microwave at a frequency of 0.1-100GHz and a power of 100-4,000W in the absence of a solvent. Further disclosed is an apparatus for preparing a metal or nonmetal phthalocyanine in the absence or presence of solvent.
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Page/Page column 15-16; 20
(2008/06/13)
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- Novel Efficient Preparative Method for Phthalocyanines from Phthalimides and Phthalic Anhydride with HMDS
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A convenient synthesis of peripherally substituted or unsubstituted phthalocyanines having a variety of metals is described. Phthalocyanines can be obtained by heating phthalimides or phthalic anhydride with metal salts, hexamethyldisilazane, a catalytic amount of p-TsOH, and DMF at 150 °C.
- Uchida, Hitoshi,Reddy, Paidi Yella,Nakamura, Shuichi,Toru, Takeshi
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p. 8736 - 8738
(2007/10/03)
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- Novel synthesis of phthalocyanines from phthalonitriles under mild conditions
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A convenient preparation of phthalocyanines from phthalonitriles was accomplished by treatment with metal salts and hexamethyldisilazane (HMDS) in DMF at 100 °C. This reaction provides a new preparative method under mild conditions for phthalocyanines having a variety of metals and substituted phthalocyanines as well as Zn-naphthalocyanine.
- Uchida, Hitoshi,Tanaka, Hirokazu,Yoshiyama, Hideyuki,Reddy, Paidi Yella,Nakamura, Shuichi,Toru, Takeshi
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p. 1649 - 1652
(2007/10/03)
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- Applications of microwave in organic synthesis: An improved one-step synthesis of metallophthalocyanines and a new modified microwave oven for dry reactions
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Metallophthalocyanine complexes are obtained quickly and efficiently by the reaction of phthalodinitrile with hydrated metallic salts without solvent and under microwave irradiation. The use of a modified commercial microwave oven to perform this type of reactions under dry conditions is described. Metallophthalocyanines and metallododecachlorophthalocyanines of some divalent metals can be also obtained from phthalic or tetrachlorophthalic anhydrides with hydrated metallic salt and urea under microwave irradiation and without solvent.
- Villemin, Didier,Hammadi, Mohamed,Hachemi, Messaoud,Bar, Nathalie
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p. 831 - 844
(2007/10/03)
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