- A novel and green route for solvothermal synthesis of manganese phthalocyanine crystals
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A novel, facile, and green route was proposed for solvothermal synthesis of manganese phthalocyanine (MnPc) crystals. The quadrangular prism-like MnPc crystals could be obtained at 190 °C during 3 h with manganese acetate and phthalodinitrile as reactants. The common ethanol was used as solvent and no other chemical additives were required in this reaction system. It is noted that purification of as prepared MnPc crystals was very simple and just required the removal of unreacted reagents washing by hot ethanol and water. Compared to the reported method, this simple synthesis route shows many advantages, such as low cost, facile preparation and purification, especially the nontoxic ethanol used as reaction medium.
- Li, Dapeng,Ge, Suxiang,Sun, Guofu,He, Qin,Huang, Baojun,Tian, Guizhong,Lu, Weiyu,Li, Guobao,Chen, Yunlong,An, Shengnan,Zheng, Zhi
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- Manganese(II) tetrasulfophthalocyanine covalently supported on natural silk: A new highly active catalyst for synthesis of benzoxazepine derivatives in water
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Natural silk as a biodegradable, biocompatible, renewable, green and abundant biomaterial was used as a support for chemical immobilization of a water-soluble manganese(II) complex with a phthalocyanine ligand possessing covalent binding ability. The prepared manganese(II) tetrasulfophthalocyanine complex supported on natural silk revealed efficient catalytic activity and reusability for the synthesis of benzoxazepine derivatives in water at room temperature.
- Hezarkhani, Zeinab,Faroghi, Mohammad Tayeb,Shaabani, Ahmad
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- Oxidation of manganese(II) phthalocyanine by molecular oxygen
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Manganese(II) phthalocyanine fails to react with oxygen when dissolved in rigorously purified, dry pyridine. Reaction does occur, however, in pure N,N-dimethylacetamide to yield a solution of an oxygen adduct. The reaction may be reversed slowly by degassing, more rapidly upon exposure to bright white light or upon addition of an electron donor in vacuo. Addition of certain electron donors, in oxygen, causes conversion to the known PcMnIII-O-MnIIIPc. This oxy-bridged species may be reconverted to the oxygen adduct by reaction with oxygen. The oxygen adduct may be isolated as a solid. Analysis, thermodynamic measurements, infrared (oxygen-18 isotopic substitution) and electronic spectra, magnetism (S = 3/2), and ESR appear consistent with the formulation (O2)MnIIIPc, a bound superoxide.
- Lever,Wilshire,Quan
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- Synthesis, structural investigations and magnetic properties of dipyridinated manganese phthalocyanine, MnPc(py)2
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The MnPc(py)2 complex was obtained in the reaction of MnPc with purified and dry pyridine under non-oxidation conditions. It crystallises in the centrosymmetric space group P21/c of the monoclinic system with two molecules per unit cell. The Mn2+ cation is coordinated by four N-isoindole atoms of phthalocyaninato(2-) macrocycle and axially by two nitrogen atoms of pyridine molecules into a tetragonal bipyramid. The MnPc(py)2 crystals are moderately stable under air, but in pyridine solution the MnPc(py)2 complex undergoes oxidation by O2 yieldings the binuclear manganese(III) μ-oxo complex (MnPcpy)2O as evidenced by the UV - Vis spectroscopy. The magnetic susceptibility measurement performed on solid sample of MnPc(py)2 shows the Curie-Weiss behaviour in the temperature region of 300-15 K. The calculated magnetic moment μeff indicates three unpaired electrons (S = 3/2), thus the ground state configuration of Mn ion is (a1g)2(eg)2(b2g) 1, and the MnPc(py)2 complex is the intermediate spin complex. Below 5.5 K (TN) the magnetic susceptibility sharply decreases due to the cooperative intermolecular antiferromagnetic interactions.
- Janczak, Jan,Kubiak, Ryszard,?led?, Ma?gorzata,Borrmann, Horst,Grin, Yuri
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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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- 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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- One-step thermal reaction of a solvent method of manganese phthalocyanine crystal
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The present invention relates to a method for one-step preparation of a manganese phthalocyanine crystal through a solvothermal reaction. The method comprises: adding phthalonitrile and manganese acetate tetrahydrate to a reaction kettle according to a molar ratio of 4:1, adding an anhydrous ethanol solution, uniformly stirring, sealing the reaction kettle, carrying out a solvothermal reaction for not less than 1 h at a temperature of 180-200 DEG C, stopping heating after completing the reaction, naturally cooling to a room temperature, taking out the prepared sample, adopting hot water and hot ethanol to repeatedly wash the remaining reactant adsorbed on the manganese phthalocyanine crystal surface, and drying to obtain the manganese phthalocyanine crystal. According to the present invention, the manganese phthalocyanine crystal prepared by using the method has the regular crystal appearance, and the whole preparation process has characteristics of simple operation, low cost, no harmful pollutant generation and easily controllable reaction process, and meets actual production requirements.
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Paragraph 0029; 0030
(2017/03/17)
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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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- Isomorphic complexes formed by recrystallisation of M(II)Pc (M(II) = Mg, Mn and Zn) in liquid 2-amino-3-picoline
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Three isomorphic, Mg, Mn and Zn phthalocyaninato complexes monoaxially ligated by 2-amino-3-picoline (2A3P) are obtained. They crystallise with 2A3P molecule as solvent molecule in the centrosymmetric space group P21/c of monoclinic system. The
- Janczak, Jan,Kubiak, Ryszard,Bukowska, Ewa
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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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- 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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- High-pressure Conditions for Improved Synthesis of Phthalocyanines
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Improved rates of formation and yields of phthalocyanines are observed when the reaction between phthalonitrile and a metal salt is carried out at pressures around 10 kbar.The reaction also benefits from the presence of a superbase, 1,5-diazabicyclonon-5-ene or 1,8-diazabicycloundec-7-ene, and a reducing agent, hydroquinone.In addition to providing superior yields of metallophthalocyanoines from a variety of metal salts, these improvements permit the synthesis of phthalocyanines otherwise difficult to obtain.High pressure combinated with a reducing agent is particularly advantageous.In the absence of a metal salt, good yields of metal-free phthalocyanine were obtained.
- Edmondson, Stephen J.,Hill, Jon S.,Isaacs, Neil S.,Mitchell, Philip C. H.
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p. 1115 - 1118
(2007/10/02)
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- (Phthalocyaninato)chromium(II)- and -manganese(II) Compounds with Pyridine, Pyrazine, and Piperidine as Axial Ligands
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(Phthalocyaninato)chromium(II) (PcCr) and -manganese(II) (PcMn) react with pyridine (py), pyrazine (pyz), and piperidine (pip) with formation of the corresponding PcML2 complexes (M = Cr, Mn; L = py, pyz, pip) which are characterized by IR, FIR, and UV/VIS spectra as well as by thermoanalytical methods.
- Hanack, Michael,Datz, Arnim
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p. 1281 - 1290
(2007/10/02)
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