- BiVO4/cobalt phthalocyanine (CoPc) nanofiber heterostructures: Synthesis, characterization and application in photodegradation of methylene blue
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BiVO4/cobalt phthalocyanine (CoPc) hierarchical nanostructures were prepared. The structural and photo-chemical properties were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron micr
- Liu, Guoshuai,Liu, Suwen,Lu, Qifang,Sun, Haiyan,Xiu, Zhiliang
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- Effect of Substituents on the Oxidation Potential of Phthalocyanines and Electrocrystallization
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A series of tetra- or octasubstituted phthalocyaninatocobalt derivatives were prepared and their oxidation behaviors were examined in relation to the nature of substituents.The oxidation potentials of phthalocyanines, especially those of rings were affected by the nature of both substituents and axial ligands.These oxidation potentials were in a linear relation with the Hammett's constants for substituents or axial ligands.The electrocrystallization proceeded when an oxidation potential higher than that for the phthalocyanine ring was given to the solution.This potential shift was therefore revealed to be an important factor to control the electrocrystallization of these phthalocyanines.
- Orihashi, Yuji,Nishikawa, Michinori,Ohno, Hiroyuki,Tsuchida, Eishun,Matsuda, Hiro,et al.
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- Thermal characterization of doped polyaniline and its composites with CoPc
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Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples.
- George, Sajan D.,Saravanan,Anantharaman,Venkatachalam,Radhakrishnan,Nampoori,Vallabhan
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p. 235201-1-235201-5
(2004)
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- Two-Channel Conductivity and Carrier Crossover in CoxNi1-x(pc)I, Alloys of the Molecular Conductors (Phthalocyaninato)nickel Iodide and (Phthalocyaninato)cobalt Iodide
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Alloys of the isostructural porphyrinic molecular conductors (phthalocyaninato)cobalt iodide, Co(pc)I, and (phthalocyaninato)nickel iodide, Ni(pc)I, of composition CoxNi1-x(pc)I, x = 0.02, 0.10, 0.15, 0.20, 0.33, 0.50, 0.75, 0.90, and 0.95, have been prepared and shown to be homogeneous solid solutions by EPR and energy-dispersive X-ray microprobe analysis.The high (?RT ca. 500 Ω-1 cm-1) metallic conductivity of Ni(pc)I (x = 0) is associated with holes (positive thermopower) created by partial oxidation from the valence ?-band of the pc macrocycle,whereas the lower (?RT ca. 50 Ω-1 cm-1) nonmetallic conductivity of Co(pc)I (x = 1) is associated with electron carriers (negative thermopower) in the partially oxidized dz2 band of the metal-ion spine.For x a maximum appears in the conductivity between 170 and 260 K.This change is attributed to paramagnetic scattering by the Co(2+) local moments.With further increase in x the conductivity continues to change smoothly toward the nonmetallic behavior of Co(pc)I.Surprisingly, the thermopower does not smoothly tend toward the large negative values for Co(pc)I but becomes increasingly positive as x is increased from 0.2 to 0.75 and begins to decrease only by x ca. 0.90.These resultsare interpreted to mean that alloys with 0.2 /ca. x /ca. 0.75-0.9 exhibit two independent conduction channels, hole carriers on the pc macrocycles and electron carriers on the metal-ion spine, and that the site of oxidation shifts progressively from the macrocycle to the metal ion as x is increased.Only by x ca. 0.95 (and T ca. 240 K) does the thermopower become negative, which signifies the crossover point beyond which all charge-transport behavior is determined by the electron carriers on the metal spine rather than the hole carriers on the macrocycle.
- Liou, Kwangkyoung,Jacobsen, Claus S.,Hoffman, Brian M.
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- Boosting the Capacitive Performance of Cobalt(II) Phthalocyanine by Non-peripheral Octamethyl Substitution for Supercapacitors?
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In this paper, pristine cobalt(II) phthalocyanine (CoPc) and non-peripheral octamethyl substituted CoPc (N-CoMe2Pc) are the focus of electrochemical investigation. CoPc and N-CoMe2Pc nanorods (NR) were synthesized by a facile precipitation process from sublimated bulk phthalocyanine powders and their electrochemical properties were explored. Due to the large specific surface area, the capacitance performance of the nanorods was significantly higher than that of the sublimated powder sample. N-CoMe2Pc powder exhibited better pseudocapacity compared with CoPc powder and CoPc NR, which is attributed to enhanced charge transfer rate and improved redox activity after the introduction of octamethyl substituents on phthalocyanine ring. The maximum specific capacitance value was achieved by N-CoMe2Pc NR based electrode, exhibiting 210.2 F g–1 capacitance at 5 mV s–1 scan rate and 156.1 F g–1 at 0.25 A g-1 current density, and also showing high efficiency and satisfactory retention. These results indicate that according to proper molecular design, N-CoMe2Pc NR could be applied as the potential candidate for electrode material in supercapacitors.
- Li, Minzhang,Ramachandran, Rajendran,Wang, Yu,Chen, Qian,Xu, Zong-Xiang
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- Preparation of Cobalt/Sulfur/Graphite Electrocatalyst for Oxygen Reduction from Efficient Two-Electron Pathway
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Abstract—: Graphite, the most stable carbon allotrope, is widely used for various applications due to its interesting properties. In the present work, graphite surface has been partially oxidized by concentrated hydrochloric acid (37%); then, the graphite oxide surface has been modified by a low-temperature method using sulfur and cobalt atoms to obtain a Co–S–GC catalyst. The current density passing through Co–S–GC catalyst has been higher than that passing through graphite. The novel cobalt-based catalyst has been demonstrated good performance for oxygen reduction reaction (ORR) due to the unique bio-inspired structure. The number of electrons transferred for ORR vary from 2.17 to 2.41 in a wide range of over-potentials indicating an effective 2-electron pathway form O2 to H2O2. The Tafel slope (≈30 mV dec–1) indicates significant amount of cobalt oxide on the surface of the catalyst. The catalyst durability test displays a negative shift of only 11.7 mV after 10 000 cycles for its half-wave potential (E1/2).
- Mohammadian,Seyyedi,Sehatnia
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- X-ray structures and homolysis of some alkylcobalt(III) phthalocyanine complexes
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The first crystallographic data for σ-bonded alkylcobalt(III) phthalocyanine complexes are reported. A single-crystal X-ray structure of CH3CH2CoIIIPc (Pc = dianion of phthalocyanine) reveals that the solid consists of centrosymmetric face-to-face dimers in which the CH3CH2CoIIIPc units retain their square pyramidal geometry. The structure appears to be the first one reported for a five-coordinate RCo(III)(chelate) complex with an electron-deficient equatorial system. The Co-C bond in CH3CH2CoIIIPc (2.031(5) A) is the longest found in five-coordinate RCo III(chel) complexes (R = simple primary alkyl group). Another X-ray study demonstrates that CH3CoIIIPc(py) has a distorted octahedral geometry with axial bonds of very similar length to those in methylcobalamin. The axial bonds are shorter than those in its octaethylporphyrin analogue, in accordance with a weaker trans axial influence in six-coordinate complexes containing an electron-deficient phthalocyanine equatorial ligand. A different trend has been observed for five-coordinate RCoIII(chel) complexes: electron-rich equatorial systems seem to make the Co-C axial bond shorter. Kinetic data for the homolysis of RCo IIIPc complexes (R = Me, Et) in dimethylacetamide are also reported. Homolysis of ethyl derivatives is faster. The Co-C bond dissociation energies (BDEs) for the pyridine adducts of the methyl and the ethyl derivative are 30 ± 1 and 29 ± 1 kcal/mol, respectively. The BDE for CH 3CoPc(py) is considerably lower than that for MeCbl despite the very similar lengths of the axial bonds in the two complexes. The results of this work do not support any correlation between the Co-C bond length and the bond strength as defined by BDE.
- Galezowski, Wlodzimierz,Kubicki, Maciej
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- Spontaneous solution-phase redox deposition of a dense cobalt(II) phthalocyanine monolayer on gold
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A dense monolayer of cobalt(II) phthalocyanine, CoPc, can be formed on a gold surface by spontaneous redox deposition followed by vacuum annealing at about 110?°C. CsCoPc(CN)2 or KCoPc(CN)2 in dilute (a??10-6 M) ethanol solution rapidly forms a dense adlayer that, when washed with ethanol, can be imaged by scanning tunneling microscopy, STM, in air. This adlayer is converted to a monolayer of CoPc by vacuum annealing as confirmed by STM and X-ray photoelectron spectroscopy (XPS). This spontaneous surface redox adsorption process represents a novel method for depositing metallorganic complexes, which are ultimately only physisorbed on gold.
- Mazur, Ursula,Leonetti, Maya,English, William A.,Hipps
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- Large-scale production of graphene by microwave synthesis and rapid cooling
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Graphene was prepared via carbonization of microwave synthesized metal phthalocyanine, followed by a rapid cooling process. The morphology and structure of the obtained graphene were controlled by the coolants.
- Xu, Zhanwei,Li, Hejun,Li, Wei,Cao, Gaoxiang,Zhang, Qinglin,Li, Kezhi,Fu, Qiangang,Wang, Jie
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- Development of a perchlorate sensor based on Co-phthalocyanine derivative by impedance spectroscopy measurements
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In this work, we have prepared a perchlorate sensor based on cobalt phthalocyanine derivative molecules. The membrane was deposited onto gold substrates using dip-coating method. Adhesion and morphological properties have been studied using contact angle measurements. Then, the sensitivity, the detection range and the detection limit were determined using electrochemical impedance spectroscopy (EIS) measurements. The sensor was also studied specificity towards interfering ions nitrate (NO3-), carbonate (CO32-) and sulfate (SO42-) to show the specificity of the membrane. The impedance behavior of the perchlorate sensor (gold/membrane) has been modeled by an equivalent electrical circuit using a modified Randles model for better understanding the phenomena present at the interface membrane/electrolyte.
- Braik,Dridi,Ali,Abbas,Ben Ali,Errachid
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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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- An innovative light assisted production of acetic acid from CO2and methanol: A first photocatalytic approach using a reusable cobalt(ii) molecular hybrid at atmospheric pressure
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Acetic acid is an important commodity chemical that is produced either by fermentation processes, or more commonly, through chemical routes such as methanol carbonylation with CO and H2, acetaldehyde oxidation, or hydrocarbon oxidation. More recently, methanol hydrocarboxylation with CO2 and H2 under thermal catalytic conditions has attracted interest. The synthesis of acetic acid from easily available CO2 is of great significance yet rarely reported. The present paper describes the first photocatalytic approach for the synthesis of acetic acid from methanol and CO2 under ambient reaction conditions without using molecular hydrogen. The maximum conversion of methanol achieved is 60% with a selectivity of 81% towards acetic acid using an octa-sulfur bound cobalt phthalocyanine (CoPc/S8) photocatalyst without an additional sacrificial electron donor. Product analysis, controlled experiments and DFT calculations suggest the formation of methylene carbene as a reactive intermediate. The developed methodology represents a potentially exciting approach for synthesizing acetic acid utilizing CO2 in a sustainable manner.
- Jain, Suman L.,Krishnamurty, Sailaja,Ray, Anjan,Saini, Sandhya,Samal, Pragnya Paramita
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supporting information
p. 9048 - 9060
(2021/11/30)
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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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- Preparation method and application of monosubstituent metal phthalocyanine derivative
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The invention provides a method for preparing a monosubstituent metal phthalocyanine derivative. According to the method, the single-substituent metal phthalocyanine derivative is prepared by directlyand fully reacting a metal salt, an organic solvent and a nitrile organic compound and is used for efficient electrocatalytic carbon dioxide reduction. The method has the following advantages: on onehand, the method is simple, few impurities exist, and the atom utilization rate is high; and on the other hand, the problems of poor product selectivity, low yield and the like caused by complex substitution reaction, more side reactions, uncertain substitution positions and quantity and other factors in the traditional preparation method are avoided.
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Paragraph 0025-0032
(2020/07/15)
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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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- Green synthesis and characterization of crystalline zinc phthalocyanine and cobalt phthalocyanine prisms by a simple solvothermal route
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A facile, environmentally-friendly and low-cost method for one-step synthesis of zinc phthalocyanine (ZnPc) and cobalt phthalocyanine (CoPc) prism-shaped crystals was proposed. The well-defined crystalline prisms (ZnPc, up to 8 mm and CoPc, more than 1 mm) can be grown during a solvothermal process at 160 °C for 6 h. It is noted that ethanol (pentanol or benzyl alcohol) was used as the reaction medium and no surfactants or other chemical additives were used in this preparation. To the best of our knowledge, this is the first report on the green and direct synthesis from simple raw materials to large ZnPc and CoPc crystals with high quality. Compared to the traditional preparation of MPc solids and their re-crystallization purification by using H2SO4, our method is very convenient, safe and time-efficient. The complete characterization, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), single crystal X-ray diffraction, powder X-ray diffraction, and Fourier transform infrared (FT-IR) and Raman spectrometry, was performed to measure the molecular structures, crystal structures, and surface morphologies. The highly predominant crystal face of ZnPc crystals was determined to be (100) and the probable crystal growth mechanism was proposed. Moreover, the thermal and photoelectric measurements of ZnPc and CoPc crystals show their excellent thermal stability and photoelectric transformation performance, respectively.
- Li, Dapeng,Ge, Suxiang,Yuan, Tianci,Gong, Jingjing,Huang, Baojun,Tie, Weiwei,He, Weiwei
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p. 2749 - 2758
(2018/05/28)
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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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- 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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- 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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- Chemically reversible reactions of hydrogen sulfide with metal phthalocyanines
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Hydrogen sulfide (H2S) is an important signaling molecule that exerts action on various bioinorganic targets. Despite this importance, few studies have investigated the differential reactivity of the physiologically relevant H2S and
- Hartle, Matthew D.,Sommer, Samantha K.,Dietrich, Stephen R.,Pluth, Michael D.
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p. 7800 - 7802
(2014/08/18)
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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 39-41
(2014/04/04)
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- Transition metal-free 1,3-dimethylimidazolium hydrogen carbonate catalyzed hydration of organonitriles to amides
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An efficient hydration of organonitriles to the corresponding amides was accomplished using 1,3-dimethylimidazolium hydrogen carbonate as an organocatalyst. The developed catalytic method was also applicable for the synthesis of metal phthalocyanines.
- Verma, Praveen Kumar,Sharma, Upendra,Bala, Manju,Kumar, Neeraj,Singh, Bikram
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p. 895 - 899
(2013/04/23)
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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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- 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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- 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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experimental part
p. 101 - 105
(2010/06/16)
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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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- Purity effects on the charge-transport properties in one-dimensional TPP[CoIII(Pc)(CN)2]2 (TPP = tetraphenylphosphonium and Pc = phthalocyaninato) conductors
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Purity effects on the temperature dependence of electrical resistivity in TPP[Co(Pc)(CN)2]2 with a typical one-dimensional metallic electronic system have been examined. In this system, no dependence on the impurity content has been observed, suggesting that the apparent thermally activated behavior is dominated by charge disproportionation.
- Yamashita, Satoshi,Naito, Toshio,Inabe, Tamotsu
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p. 692 - 694
(2009/12/06)
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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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- 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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- 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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- 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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p. 179 - 188
(2007/10/03)
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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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- Stereochemistry and properties of the M(II)-N(py) coordination bond in the low-spin dipyridinated iron(II) and cobalt(II) phthalocyanines
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A comparison between the coordination bond M(II)-N(py) and vibrational properties and stereochemistry of the dipyridinated iron(II) and cobalt(II) phthalocyaninato complexes, FePc(py)2 and CoPc(py)2 (Pc=C32H16N8, py=C5H5N), is carried out using the single crystal X-ray diffraction and the vibrational spectroscopy. Both dipyridinated complexes have been synthesized in crystalline form by heating of the β-FePc or β-CoPc in pyridine at 160°C. The crystals are formed during the slowly cooling process. The crystal of FePc(py)2 and CoPc(py)2 are isostructural. They crystallize in the space group P21/c of the monoclinic system with two molecules per unit cell. The structural results and coordination bond properties are strictly related in these complexes. The Fe2+ and Co2+ cations are coordinated by four N-isoindole atoms of the phthalocyaninato(2-) macrocycle and axially by two nitrogen atoms of pyridine molecules to form a tetragonal bypyramid. The vibrational M-Nisoindole parameters are much more affected than the corresponding structural parameters by the difference in the electronic structure of the Co and Fe. The axial M(II)-N(py) bond length depends strongly on the electron configuration of the central metal. The value of the M(II)-N(py) bond length of 2.039(2) A? in FePc(py)2 and 2.340(2) A? in CoPc(py)2 clearly evidences on the localization of the unpaired electron on the dz2 orbital of the Co in the cobalt complex. The electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements have also detected the unpaired electron in the molecule of CoPc(py)2. EPR and magnetic susceptibility measurements performed on a solid sample of FePc(py)2 shown on its diamagnetic character. The importance of the d(π)→π*(Pc) back donation is manifested in the difference between the values of the C-Nisoindole and C-Nazamethine bond lengths of the Pc macrocycle.
- Janczak, Jan,Kubiak, Ryszard
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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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- Methyl transfer from methylcobalt(III) phthalocyanine to bromide and iodide ions in sulfolane
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Rates of methyl transfer from methylcobalt(III) phthalocyanine (MeCoIIIPc) to bromide and iodide nucleophiles in sulfolane were measured in the temperature range 20-40°C. In contrast to iodide, bromide ion forms an unreactive complex MeCoIIIPcBr-, formation constant for which was determined. Rates of reaction between CoIPc- and methyl iodide were also measured. Identity rate constant for methyl transfer between two CoIPc- nucleophiles of 51 M-1 s-1 at 25°C was obtained using the Marcus equation. This identity rate is the largest out of many determined in this solvent.
- Galezowski
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p. 949 - 955
(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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- Syntheses and Characterization of Bromo- and Chloro(phthalocyaninato)bismuth(III) Complexes
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By the reactions of BiX3 (X=Cl-, Br-, I-, and NO3-) with Li2(pc) (pc=phthalocyaninate dianion, C32H16N82-) in dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, and acetone, complexes have been produced.These complexes were also produced by heating a mixture of BiX3 and phthalonitrile.Among them, and were isolated for the first time as a phthalocyanine complex of group-15 elements and successfully characterized by elemental analyses, solution chemistry, electronic and IR spectroscopy.The latter two complexes were soluble in polar solvents, but were insoluble in nonpolar solvents.In solutions, bismuth(III) in was labile and was readily expelled from a pc ring by a trace amount of water, acids, and bases, and it was replaced by a divalent transition metal upon the addition of MSO4 (M=cobalt(II), nickel(II), copper(II), and zinc(II) forming .The electronic and IR spectra of the s were characteristic of the usual metallophthalocyanines, except that a hyper metal-to-ligand charge-transfer band appeared in their electronic spectra.
- Isago, Hiroaki,Kagaya, Yutaka
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p. 383 - 389
(2007/10/02)
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- Methyl transfers. 15. CoIPc- as a nucleophile and leaving group
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Many complexes of cobalt in the +1 oxidation state are excellent nucleophiles. The complex with phthalocyanine, Pc2-, is an example; the rates of reaction of complex (CoIPc)-, 1-, with MeI and other alkylating agents in dimethylacetamide (DMA) solution are reported. In contrast to previous studies with other Co(I) complexes, the rate of reaction of the methylated product, (MeCoIIIPc, 3) with I- is also readily measured, allowing a kinetic evaluation of the equilibrium constant K = [1-][MeI]/[3][I-] = 0.004 in DMA at 25 °C. Similarly, Br- also reacts with 3 reversibly, and the rate and equilibrium constants are reported. Thus 1- is also a good leaving group. With CN, 3 gives complex MeCoIIIPcCN- reversibly and slowly gives MeCN in a reaction zero order in CN-. The fast identity rate constants for I- attack on MeI as well as that for Br- attack on MeI are given. Two different paths to the identity methyl transfer rate constant, kCoCo, for the 1- + 3 reaction with use of the Marcus equation gave kCoCo = 4.4 M-1 s-1 from the 3 + I- data but kCoCo = 0.088 M-1 s-1 from the 3 + Br- data. This discrepancy, which is outside of experimental error, constitutes a deviation from the Marcus treatment; it is discussed.
- Galezowski, Wlodzimierz,Ibrahim, Prabha N.,Lewis, Edward S.
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p. 8660 - 8668
(2007/10/02)
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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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- Synthesis and Properties of (Phtalocyaninato)cobalt(II) Adducts with Nitrogen Bases
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(α-) and (β-phtalocyaninato)cobalt(II) (PcCo) are treated with ligands L = pyrazine (pyz), 4-methylpyrazine (4-mepyz), pyridine (py), pyridine-d5 (py-d5), 4,4'-bipyridine (bpy), and n-butylamine (bu).The PcCo adducts PcCoL obtained (L = pyz, mepyz, me2pyz, Clpyz, py, py-d5, bu); PcCo-L-CoPc (L = bpy), n (L = pyz); PcCoL2 (L = pyz, py py-d5, pip, bpy), are characterized by ESR spectroscopy, thermal and magnetic measurements.Pentacoordinated complexes PcCoL are formed preferentially.Hexacoordinated complexes PcCoL2 with L = py, 4-mepy, bpy, pyz, piperidine (pip) are only formed at a high ligand concentration.While the polymer n was isolated as a stable compound, attempts to obtain n were unsuccessful.With 1,4-diazabicyclooctane (dabco), a strong ?-donor ligand, n is easily formed.In addition, the reaction of PcCo with 1,6-naphthyridine (naph), benzyl isocyanide (bzNC), and 1,4-diisocyanobenzene (dib) was also investigated.
- Metz, Josef,Hanack, Michael
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p. 1307 - 1314
(2007/10/02)
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- Stability of the Cobalt Complexes of Tetrazaporphyrins and Mechanism of Their Dissociation in Sulphuric Acid
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We have studied the solvoprotolytic dissociation of the cobalt complexes of tetrazaporphyrin and tetra(tetramethylene)terazaporphyrin in aqueous sulphuric acid solutions.A clearer representation of the dissociation mechanism of metal porphyrins has been obtained.
- Berezin, B. D.,Khelevina, O. G.,Stuzhin, P. A.,Glazunov, A. V.
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p. 1311 - 1314
(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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