- Unveiling the genesis of the high catalytic activity in nickel phthalocyanine for electrochemical ammonia synthesis
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Electrochemical ammonia synthesis by the nitrogen reduction reaction (NRR) using an economically efficient electrocatalyst can provide a substitute for the Haber-Bosch process. However, identification of active sites responsible for the origin of catalytic activity in transition metal phthalocyanine is a difficult task due to its complex structure. Herein, density functional theory (DFT) is applied to identify the probable active sites of nickel phthalocyanine (NiPc) for the NRR as well as the origin of catalytic activity which is associated with the d band center and density of states (DOS) of Ni in NiPc. Accordingly, NiPc nanorods (NRs), synthesized by a solvothermal method in large scale, exhibit an NH3yield rate about 85 μg h?1mgcat?1and a faradaic efficiency (FE) of 25% at ?0.3 Vvs.RHE. Moreover, the catalyst shows long term stability up to 30 hours while maintaining the NH3yield and FE. The isotopic labelling experiment and other control investigation led to validation of the nitrogen source in NH3formation. This study provides brand new insightful understanding of the active sites and the origin of the catalytic activity of NiPc for their NRR applications.
- Bhattacharyya, Dibyendu,Chattopadhyay, Santanu,Ghorai, Uttam Kumar,Jha, Shambhu N.,Kapse, Samadhan,Murmu, Shyamal,N., Abharana,Paul, Sourav,Thapa, Ranjit
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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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- UNUSUAL BAND-FILLING AND COUNTERION ORDERING EFFECTS IN A PHTHALOCYANINE MOLECULAR METAL. SINGLE CRYSTAL STUDIES OF Ni(Pc)(ClO//4)//y.
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We report here single crystal structural, charge transport, and optical studies of the metallophthalocyanine 'metal' Ni(Pc)(ClO//4)//y, y equals 0. 42**4**,**5, which provide the first detailed glimpse of how the collective properties of a molecular left bracket M(Pc)** plus ** rho right bracket X// rho ** minus material vary in an essentially isostructural series as rho is displaced from the more typical value of minus 0. 33**1**2. We also report here a counterion order-disorder transition which is unprecedented for a phthalocyanine conductor and evidence that caution must be exercised in reporting left bracket M(Pc)** plus ** rho right bracket X// rho ** minus stoichiometries based upon analyses of bulk (multicrystal) samples.
- Almeida, M.,Kanatzidis, M. G.,Tonge, L. M.,Marks, T. J.,Marcy, H. O.,et al.
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- Complexes derived from Phthalonitrile. The Intermediates to Nickel Phthalocyaninate
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The formation of (pc = phthalocyaninate) through the stepwise reactions of nickel ion and phthalonitrile in a two-compartment electrolyzer separated with an ion-exhange membrane is traced.Five reaction intermediates, which readily convert to upon heating, were isolated by means of preparative thin-layer chromatography and characterised mass spectrometrically.
- Yang, Chiu Her,Chang, Chau-ting
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- Solventothermal synthesis and X-ray crystal structures of two nickel complexes with novel alkoxy-substituted phthalocyanine ligands
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Solventothermal reactions of nickel acetate tetrahydrate with 1,2-dicyanobenzene in methanol and ethanol yield novel complexes in which nickel atoms are coordinated by modified phthalocyanine ligands with inner rings bearing methoxy and ethoxy substituents, respectively.
- Molek,Halfen,Loe,McGaff
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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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- 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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- An efficient synthesis of phthalocyanines based on an unprecedented double-addition of oximes to phthalonitriles
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A novel and efficient method is reported for the preparation of phthalocyanines from phthalonitrile or its derivatives which utilizes low-cost reagents of hydrolytic stability, high simplicity, and easy accessibility, i.e., oximes, and proceeds via an unprecedented double addition of oximes to the nitrile group. Copyright
- Kopylovich, Maximilian N.,Kukushkin, Vadim Yu.,Haukka, Matti,Luzyanin, Konstantin V.,Pombeiro, Armando J. L.
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- Electronic and magnetic properties of Ni nanoparticles embedded in various organic semiconductor matrices
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Ni nanoparticles with a size distribution from 2 to 6 nm, embedded in various organic matrices, were fabricated in ultrahigh vacuum. For this purpose metal free and Ni phthalocyanine, fullerene C60, and pentacene were coevaporated with Ni. When
- Br?uer, Bj?rn,Vaynzof, Yana,Zhao, Wei,Kahn, Antoine,Li, Wen,Zahn, Dietrich R.T.,De Julián Fernández, César,Sangregorio, Claudio,Salvan, Georgeta
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- Accurate molecular structure of nickel phthalocyanine (NiN 8C32H16): Gas-phase electron diffraction and quantum-chemical calculations
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The molecular structure of the nickel phthalocyanine (NiPc) was determined using the combination of gas-phase electron diffraction (GED), mass spectrometry and quantum chemical calculations. The DFT calculations with employing different functionals and ba
- Tverdova, Natalya V.,Pimenov, Oleg A.,Girichev, Georgiy V.,Shlykov, Sergey A.,Giricheva, Nina I.,Mayzlish, Vladimir E.,Koifman, Oscar I.
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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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- 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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- 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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- 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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- 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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- 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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- 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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- 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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- Novel and mild route to phthalocyanines and 3-iminoisoindolin1-ones via N,N-diethylhydroxylamine-promoted conversion of phthalonitriles and a dramatic solvent-dependence of the reaction
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Refluxing a mixture of phthalonitrile C6R1R 2R3R4(CN)2 1 (R1-R 4 = H), or its substituted derivatives 2 (R1, R 3, R4 = H, R2 = Me), or 3 (R1, R4 = H, R2, R3 = Cl) (lequiv.) and N,N-diethylhy-droxylamine, Et2NOH, (4 equivs.) in methanol for 4 h results (Route A) in precipitation of the symmetrical (6 and 8) and an isomeric mixture of unsymmetrical (7) phthalocyanines, isolated in good (55-65 % ) yields. The reaction of phthalonitriles 1, 2, or 4 (R1, R 3, R4 = H, R2 = NO2) (4 equivs.) with Et2NOH (8 equivs.) in the presence of a metal salt MCl 2 (M = Zn, Cd, Co, Ni) (1 equiv.) in n-BuOH or without solvent results in the formation of metallated phthalocyanine species (9-17). Upon refluxing in freshlydistilled dry chloroform, phthalonitrile 1 or its substituted analogues 2, 3 or 5 (R1-R4 = F) (1 equiv.) react with N,N-diethylhydroxylamine (2 equivs.) affording 3-iminoisoindolin-1- ones 18-21 (Route B) isolated in good yields (55-80%). All the prepared compounds were characterized with C, H, and N elemental analyses, ESI-MS, IR, and compounds 18-21 also by ID (1H, 13C(1H]), and 2D (1H,15N-HMBC and 1H,13CHMQC, 1H,13C-HMBC) NMR spectroscopy.
- Luzyanin, Konstantin V.,Kukushkin, Vadim Yu.,Kopylovich, Maximilian N.,Nazarov, Alexey A.,Galanski, Markus,Pombeiro, Armando J. L.
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scheme or table
p. 135 - 142
(2009/04/07)
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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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- 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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- COLOR FILTER
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The present invention provides a color filter which is more durable than a dye-type color filter and also has green pixel portions which exhibit a bright green color having a strong yellowish tinge when used in a liquid crystal display device using a three-band lamp having a main emission line of green light of about 545 nm as a light source, thus enabling the liquid crystal display device to display bright images even when using a backlighting light source having a low intensity. This color filter comprises green pixel portions which (1) contain a halogenated metal phthalocyanine dye wherein 8 to 16 halogen atoms are bonded to benzene rings in one phthalocyanine molecule, and (2) exhibit maximum transmittance at a wavelength within a range from 520 nm to 590 nm with respect to the transmission spectra of the entire range of visible light.
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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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- Novel Tribenzhexaazaporphyrins as Unsymmetric Phthalocyanine Analogues
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The formal substitution of one isoindole subunit of a phthalocyanine by a 1,2,4-triazole moiety afforded a new family of unsymmetric azaporphyrins - of which compounds 1 and 2 are representative - with potential nonlinear optical properties.
- Fernandez-Lazaro, Fernando,Sastre, Angela,Torres, Tomas
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p. 1525 - 1526
(2007/10/02)
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- Process for producing metal phthalocyanine pigment
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A process for producing a metal phthalocyanine pigment which comprises the steps of: reacting phthalic anhydride or a derivative thereof with urea or a derivative thereof with heating in the presence of a catalyst either in the presence or absence of an organic solvent; adding to the reaction mixture of the preceding step a metal or its compound capable of constituting the core of the metal phthalocyanine either alone or together with urea or a derivative thereof, without isolating the reaction product from the reaction mixture of the preceding step; and allowing the reaction mixture to react while simultaneously applying a mechanical grinding force in the presence or absence of a grinding agent.
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- Reactive dyes having a sulphonamido group
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A water soluble dye having a reactive group of the formula: STR1 wherein: T is a labile atom or group; and R2 and R3 are each independently a non-chromophoric optionally substituted aryl or alkyl group.
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- Synthesis of high-purity phthalocyanines (pc): High intrinsic conductivities in the molecular conductors H2(pc)I and Ni(pc)I
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We show that one can prepare M(pc)I crystals, M = H2 and Ni, with remarkably improved charge-transport properties by carefully avoiding impurities in the preparation of the M(pc) precursors. The purest H2(pc) (a melt method in quartz and Teflon vessels while very pure Ni(pc) (170-250 ppm) could only be obtained by metalation of the pure H2(pc). Template syntheses of Ni(pc) result in impure material and are to be discouraged for applications requiring very pure M(pc) materials. H2(Pc)I and Ni(pc)I synthesized from the high-purity precursors remain metallic down to ca. 3 K, a far lower temperature than ever before observed. At this temperature the conductivities exhibit maximum values that are ca. 30-fold greater than at room temperature, not 5-7-fold as seen before, with absolute values of σ ~ (1-2) × 104 Ω-1 cm-1. The study of a series of Ni(pc)I compounds prepared from Ni(pc) parent materials exhibiting a range of purity levels further shows a strong correlation between the charge-transport properties and the level of paramagnetic impurities in the macrocycle precursor. However, the maximum conductivity appears to saturate at the lowest impurity concentrations, which suggests that the behavior exhibited by the best materials prepared are representative for the first time of the limiting, intrinsic charge-transport properties of H2(pc)I and Ni(pc)I. A full structure report for H2(pc)I-1 is presented also. The structure consists of metal-over-metal stacks of partially oxidized H2(pc) groups surrounded by linear chains of triiodide anions. The two H2(pc) molecules within a unit cell are staggered by 40°. H2(pc)I crystallizes with two formula units in the tetragonal space group D24h-P4/mcc with a = 13.931(2) A?, c = 6.411(1) A?, and V = 1244.2(6) A?3 (T = 108 K).
- Thompson, Julia A.,Murata, Kazuhiko,Miller, Douglas C.,Stanton, Judith L.,Broderick, William E.,Hoffman, Brian M.,Ibers, James A.
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p. 3546 - 3553
(2008/10/08)
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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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- Electrosynthesis and Resonance-Raman Spectrum of Phthalocyaninatoiron(II)
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The electrosynthesis of phthalocyanine complexes of iron, cobalt, nickel, and copper has been carried out and the method provides a facile, one-stage, room-temperature preparation.The electronic and i.r. spectra have been studied for all four complexes and resonance-Raman data are presented also for dissolved in aniline.Excitation profiles based on the electronic absorption band of at 606 nm suggest that this electronic absorption is a vibronic shoulder on the side of the main electronic (0-0) transition at 668 nm.
- Griffiths, Lynne,Straughan, Brian P.,Gardiner, Derek J.
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p. 1193 - 1196
(2007/10/02)
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- SYNTHESIS OF METALLOPHTHALOCYANINES FROM PHTALONITRILE WITH STRONG ORGANIC BASES
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Several metallophthalocyanines (MPc: M=Ni(II), Co(II), Zn(II), Pb(II), Fe(II), Sn(II), Cd(II), Mg(II), and Mn(III)) were obtained by heating phthalonitrile with metal salts in alcohols in the presence of 1,8-diazabicycloundec-7-ene.Metal acetylacet
- Tomoda, Haruhiko,Saito, Shojiro,Shiraishi, Shinsaku
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p. 313 - 316
(2007/10/02)
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