- The solid phase, room-temperature synthesis of metal-free and metallophthalocyanines, particularly of 2,3,9,10,16,17,23,24-octacyanophthalocyanines
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Room-temperature synthesis of phthalocyanines (pcs) by condensation of phthalonitriles in the presence of solid sodium methoxide in THF is proposed for the synthesis of metal-free pcs with temperature- and/or base-sensitive substituents. The addition of metal salts after metal-free pc formation in the same vessel produces metallopcs in moderate to high (ca. 30-90%) yields.
- Nemykin, Victor N.,Kobayashi, Nagao,Mytsyk, Vladislav M.,Volkov, Sergey V.
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- Synthesis and Aggregation Studies of Functional Binaphthyl-Bridged Chiral Phthalocyanines
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We describe the preparation of a battery of chiral Zn(II) phthalocyanines with an AABB substitution pattern through cross-condensation of different chiral, binaphthyloxy-linked bisphthalonitriles and (non)functionalized single phthalonitriles. All the compounds are endowed with reactive groups (halogen and/or ethynyl moieties) that will allow us to prepare customized amphiphilic phthalocyanines. Preliminary self-assembly studies in solution have been performed by UV-vis and circular dichroism experiments.
- Revuelta-Maza, Miguel á.,Torres, Tomás,Torre, Gema De La
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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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- Synthesis, crystal structure and characterization of a new zinc phthalocyanine complex
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A new complex [ZnPc(H2O)]·2DMF (1), where Pc = phthalocyanine and DMF = N,N-dimethylformamide, has been synthesized and its crystal has been determined by single-crystal X-ray diffraction method. The compound crystallizes in the triclinic space group P - 1. The lattice parameters are a = 11.668(5) A?, b = 12.186(5) A?, c = 13.939(6) A?, α = 78.697(7)°, β = 88.045 (7)°, γ = 62.949(7)°, V = 1727.4(12) A?3 and Z = 2. The Zn(II) ion is five-coordinated by four nitrogen atoms from Pc ligands and one oxygen atom from one water molecule. Notably, there are strong π-π interactions between Pc ligands, leading to 1D superamolecular structure. Moreover, the elemental analyses, FT-IR, UV-vis and Fluorescence spectra for this complex were also determined.
- Cui, Li-Ying,Yang, Jin,Fu, Qiang,Zhao, Bao-Zhong,Tian, Lei,Yu, Hai-Ling
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- Electrochemistry of metal phthalocyanines in organic solvents at variable pressure
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High-pressure electrochemical investigations of representative metallophthalocyanines in solution are reported. The selected systems were ZnPc, CoPc, FePc, and CoTNPc (Pc = phthalocyanine, TNPc = tetraneopentoxyphthalocyanine) in several donor solvents and (for CoTNPc) dichlorobenzene, with [Bu4N][ClO4] as supporting electrolyte and a conventional Pt electrode referred to Ag+(CH 3CN)/Ag. Electrode reaction volumes ΔVcell for CoTNPc and ZnPc show that consecutive ring reductions result in progressive increases in electrostriction of solvent in accordance with Drude-Nernst theory. Reductions of the metal center in CoTNPc and CoPc, however, result in much less negative values of ΔVcell than would be expected by analogy with ring reductions of the same charge type. This is attributable to loss of axial ligands following the insertion of antibonding 3dz2 electrons on going from CoIII to low-spin CoII and then CoI. In the same vein, rate constants for reduction of Co III centers to CoII were an order of magnitude slower than those for other metal center or phthalocyanine ring reductions because of Franck-Condon restrictions. The volumes of activation ΔV el? were invariably positive for all the electrode reactions and in most cases were roughly equal to the volumes of activation for reactant diffusion ΔVdiff?, indicating predominant rate control by solvent dynamics rather than by activation in the manner of transition-state theory for which negative ΔVel? values are expected. For CoTNPc and CoPc in donor solvents, the ΔVcell and ΔVel? data are consistent with the assignments of the successive reduction steps made for CoTNPc in DMF by Nevin et al. (Inorg. Chem. 1987, 26, 570).
- Yu, Bazhang,Lever,Swaddle, Thomas W.
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- Electronic energy levels of organic dyes on silicon: A photoelectron spectroscopy study of ZnPc, F16ZnPc, and ZnTPP on p-Si(111):H
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Alignment of energy levels and chemical interaction of the organic pigments ZnPc, substituted F16ZnPc, and ZnTPP on H-terminated Si(111) have been deduced from valence band and core level photoelectron spectroscopy with high surface sensitivity for coverage below and in the monolayer region. Hydrogen-terminated Si(111) was prepared in UHV. The dyes have been purified by zone sublimation and were deposited at room temperature by PVD. SXPS taken at the synchrotron BESSY shows physisorption of the dye molecules; chemical shifts indicating strong interactions with the substrate have not been observed. The maxima of the HOMO photoemission of ZnPc, F16ZnPc, and ZnTPP are measured at 0.45, 1.55, and 1.0 eV below the Si valence band maximum. These experimental values are compared to theoretical values and are related to the position of the optical gap, the transport gap, and the redox potentials of the ground and excited state.
- Weiler, Ulrich,Mayer, Thomas,Jaegermann, Wolfram,Kelting, Christian,Schlettwein, Derck,Makarov, Sergey,Woì?hrle, Dieter
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- Zn phthalocyanine/carbon nitride heterojunction for visible light photoelectrocatalytic conversion of CO2 to methanol
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Zinc phthalocyanine/carbon nitride nanosheets photoelectrocatalysts were obtained by evaporation and calcination of the mixture of ZnPc and carbon nitride. It exhibits highly efficient synergistic function between PC-CO2RR and EC-CO2RR. The energy band matching between the ZnPc and carbon nitride results in the faster electrons transfer and less electron-hole pairs recombination. The optimized ZnPc/carbon nitride at a ratio of 0.1 wt% demonstrates high efficiency in photoelectrocalytic reduction of CO2 under visible light, generating a major product of methanol at a yield of 13 μmol·cm?2 after 8 h. The efficiency of photoelectrocalytic reduction of CO2 to methanol is 2.6 times as high as that of electrocatalytic CO2 reduction reaction, and 5.9 times as high as that of photocatalytic CO2 reduction reaction. The mechanism of the photoelectrocatalytic CO2 reduction reaction to methanol was discussed in detail.
- Zheng, Jingui,Li, Xiaojie,Qin, Yuhu,Zhang, Shuqin,Sun, Mingsheng,Duan, Xiaoguang,Sun, Hongqi,Li, Peiqiang,Wang, Shaobin
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- Preparation of non-substituted metal phthalocyanines at low temperature using activated Rieke zinc and magnesium
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Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various alcohols in presence of chemically activated Rieke zinc and magnesium in three forms (ordinary magnesium turnings, activated Rieke magnesium and complex Mg(anthracene)·3THF) at low temperatures (20-50°C) is described. It is shown that the presence of active elemental metal causes a rapid PcM formation in low-weight alcohols. Copyright
- Kharisov,Garza-Rodriguez,Leija Gutierrez,Ortiz Mendez,Garcia Caballero,Tsivadze
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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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- Zinc phthalocyanine coupled with UIO-66 (NH2) via a facile condensation process for enhanced visible-light-driven photocatalysis
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Metal-organic frameworks (MOFs) have shown a great potential for water treatment as an environmentally friendly photocatalyst. In this work, a zirconium based MOF, UIO-66 (NH2) covalently coupled with zinc phthalocyanine (ZnTCPc) was prepared via a facile condensation process. Compared with the mixture of ZnTCPc and UIO-66 (Zr) by impregnation, ZnTCPc/UIO-66 (NH2) presented an enhanced photocatalytic activity for the degradation of methylene blue (MB) under visible-light irradiation. The formation of strong covalent bonds and synergistic integration between ZnTCPc and UIO-66 (NH2) was proved by characterization results such as transmission electron microscopy, X-ray photoelectron spectra and Fourier transform infrared spectroscopy. Additionally, ZnTCPc/UIO-66 (NH2) photocatalyst retained excellent stability after five recycles, and the photocatalytic mechanism was investigated systematically. This work demonstrates a high potential of using porous MOFs-based materials not only as supports but as electron acceptors to trigger the reaction for coupling MOFs with dye, fabricating novel MOFs-dye nanocomposite systems and enhancing their photostability and photocatalytic activity.
- Liang, Qian,Zhang, Miao,Zhang, Zhihui,Liu, Changhai,Xu, Song,Li, Zhongyu
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- Phthalocyanization of Cadmium Sulfide and Zinc Oxide. Effects on the Photochemistry in Aqueous Dispersion
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A novel method for the synthesis of metal phthalocyanines on inorganic semiconductive powders is described.Coverage roughly equivalent to a monolayer is achieved for cadmium phthalocyanine on CdS and zinc phthalocyanine on ZnO.This surface modification increases the quantum efficiency, Φ, for H2O2 generation in CdPC/CdS up to a factor of 3 while reducing Φ by a factor of 2 in the ZnPC/ZnO.These results are discussed in relation to surface states and O2 adsorption.In the donor-free cases, photodissolution is still observed with the phthalocyanized powders.Although the phthalocyanines do not sensitize H2O2 formation, ESR results reveal that charge transfer does occur between ZnPC and ZnO.
- Harbour, John R.,Dietelbach, Bonita,Duff, James
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- Photoelectron spectroscopy on thin films of extended zinc porphyrazines
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Photoemission measurements were performed on a series of stepwise benzoannelated zinc porphyrazine molecules in thin films. The electronic structure of tert-butyl-substituted zinc tetraazaporphyrin, phthalocyanine, and naphthalocyanine is investigated using mainly EUV synchrotron radiation. A detailed analysis of the zinc satellites in the spectra of the valence region is performed in an attempt to infer the effect of ligand size extension on the metal-ligand interactions. No differences in the character of the bond between zinc and ligand were detected as a function of ligand size. The results are compared with those for the respective metal-free and copper-containing molecules.
- Pop,Winter,Freyer,Widdra,Hertel
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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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- 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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- Coordination properties of diethylenetriamine in relation to zinc phthalocyanine
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The coordination properties of diethylenetriamine (DETA) as a ligand containing three donor nitrogen atoms, two terminal primary amino groups and one secondary central amino group, with respect to divalent zinc ion in ZnPc were examined. The ZnPcDETA complex in the powder form was obtained by the solvothermal reaction of ZnPc with DETA. Recrystallization of the crude product from 3,4-lutidine yields non-centrosymmetric monoclinic solvated crystals (ZnPcDETA)3·3,4-lut (1) with the space group of Cc. As show the X-ray single crystal analysis in ZnPcDETA complex, the DETA coordinates via terminal amine group to the divalent zinc ion of a planar ZnPc molecule in axial position. Interaction of the N atom of DETA containing a lone electron pair with divalent zinc ion of ZnPc and the formation of the Zn-N coordination bond leads to deviation of the Zn from the N4-isoindole plane of Pc by ~ 0.5 ? toward the N-atom of the axial DETA ligand as well as to saucer-shaped distortion of the Pc macrocycle. Arrangement of ZnPcDETA molecules in the 3,4-lutidine solvate crystal with the composition of (ZnPcDETA)3·(3,4-lutidine) - (1) is determined by the van der Waals forces and by the weak N–H?N hydrogen bonds. The lack of the π?π interaction between the phthalocyaninate(2-) macrocycles in the crystals (1) is clearly evidenced by the Hirshfeld surface analysis, and increases significantly their solubility in most common solvents, even in water, when comparing to the parent ZnPc pigment with limited solubility in solvents and insoluble in water. This feature together with the strong absorption in the therapeutic window within the 600–900 nm makes it a potentially good photosensitizer. DFT calculations performed for the ZnPc-derivatives with DETA, coordinated via terminal or central amine group of DETA as well as for the bridged complex (through the terminal amino groups of the DETA ligand of two ZnPc molecules) show the possibility to obtain all three of these complexes. UV–Vis absorption spectra ZnPcDETA complex (1) in solutions as well as the diffuse reflectance spectroscopy (DSR) supported by the TD-DFT calculations were used for the characterization of the spectroscopic properties. SHG efficiency of 1 is ~10% in relation to that of KDP.
- Janczak, Jan
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- Solvent Effects on Crystal Growth and Transformation of Zinc Phthalocyanine
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The process of α --> β crystal transformation of zinc phthalocyanine in vapor of the various alcohols was studied by means of X-ray diffractometry and electron microscopy.The existence of the intermediate crystal form through which the α form transformed
- Iwatsu, Fumio,Kobayashi, Takashi,Uyeda, Natsu
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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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- 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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- Comparative study of beryllium, magnesium and zinc phthalocyanine complexes with 4-picoline
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Three new Be(II), Mg(II) and Zn(II) phthalocyaninato(2-) complexes with 4-picoline (4-Mepy) in the crystalline form have been obtained by recrystallization of the respective M(II)Pc in 4-picoline under water-free conditions. BePc and ZnPc in 4-picoline solution form 4 + 1 coordinated complexes, while the 4-Mepy molecules biaxially ligate MgPc. The planar phthalocyaninato(2-) macroring of BePc and ZnPc upon mono-axial ligation by the 4-Mepy molecule adopts the saucer-shape form. The interaction of the central M(II) with the ligated 4-Mepy molecule leads to a deviation of the metal from the centre cavity by ～0.31 ? and ～0.35 ? in the Be and Zn phthalocyaninato complexes, respectively. In MgPc, the Pc ring upon biaxial ligation retains a planar configuration. The axial M(II)-N(4-Mepy) bond is longer than the four equatorial M(II)-Niso bonds in Mg and Zn phthalocyaninato complexes, while in the Be complex the opposite relation between the axial and equatorial Be-N bonds is observed. Thermogravimetric analysis for all these compounds exhibits only one slope down, due to the loss of 4-Mepy molecules from the complexes, which transform finally into the respective M(II)Pc complexes in the β-form.
- Kubiak,Janczak,?led?,Bukowska
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- Rational design of a reactive yet stable organic-based photocatalyst
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Zinc perfluoro-fluoroalkyl-phthalocyanine, synthesized in high yield, does not exhibit electron loss, does not aggregate in solution, is photostable and produces 1O2 in very high quantum yields. Aerobic photo-oxygenation of an external substrate occurs without catalyst self-oxidation. The encapsulation of a metal center in a refractory organic environment could guide the design of other viable catalysts for oxygenation of substrates either for synthesis or for oxidative destruction of organic or biological molecules, under reaction conditions that include the use of only air and light. The Royal Society of Chemistry 2009.
- Gerdes, Robert,Lapok, Lukasz,Tsaryova, Olga,Woehrle, Dieter,Gorun, Sergiu M.
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- Fluorinated phthalocyanines as molecular semiconductor thin films
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Thin films of pefluorinated phthalocyanines F16Pc show promise as molecular semiconductors in organic field effect transistors. A review is provided of growth studies and electrical characterization of presently discussed materials. Using this state-of-the-art as a starting point the synthesis and position of energy levels of partly fluorinated Zn(II) phthalocyanines is described. Growth characteristics of vapour-deposited thin films on inorganic and organic dielectrics are studied. Possibilities to use fluorinated phthalocyanines in technical applications of OFET are discussed.
- Brinkmann,Kelting,Makarov,Tsaryova,Schnurpfeil,Woehrle,Schlettwein
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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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- Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
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In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
- Hosseini-Sarvari, Mona,Koohgard, Mehdi
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p. 5905 - 5911
(2021/07/12)
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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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- Preparation method of zinc phthalocyanine
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The invention provides a preparation method of zinc phthalocyanine. The preparation method sequentially comprises the following steps that firstly, phthalonitrile is dissolved in a solvent and then loaded into a first raw material storage tank for use; secondly, zinc salt is put into an agate grinding bowl to be ground fine, and a certain amount of zinc salt is taken, dissolved in a solvent and then loaded into a second raw material storage tank for use; a temperature control and pressure system is turned on, reaction temperature and pressure are set, a microwave system is turned on, the volume flow rate of feed is calculated according to the mole ratio of phthalonitrile to zinc acetate dihydrate, the flow rates of a first liquid metering pump and a second liquid metering pump are set, thefirst liquid metering pump and the second liquid metering pump are simultaneously turned on and connected, and solutions in the first storage tank and the second storage tank are mixed at a Y-type mixing joint separately and then enter a microchannel reactor; after a period of a residence reaction, material liquid is collected into a collection tank, the material liquid in the collection tank ispumped into a crystallization tank, after the liquid is cooled to the room temperature, water is added with the volume ratio of 1:1, beating is conducted, and a lot of solids are precipitated; the material liquid is cooled to -5-0 DEG C through an ice-salt bath, and stirring crystallization is conducted for 5 hours; extraction filtration under reduced pressure is conducted, filter cakes are rinsedwith water, and drying is conducted to obtain the product zinc phthalocyanine.
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Paragraph 0033; 0034; 0035; 0036; 0037-0044
(2019/03/25)
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- Enhanced anti-microbial effect through cationization of a mono-triazatricyclodecane substituted asymmetric phthalocyanine
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Antimicrobial photodynamic therapy (aPDT) is an effective way to combat infectious diseases and antibiotic resistance. Photosensitizer is a key factor of aPDT and has triggered extensive research interest. In this study, a new asymmetric Zn(II) phthalocyanine mono-substituted with a triazatricyclodecane moiety (compound 3) and its cationic N-methylated derivative (compound 4) were synthesized. Their photodynamic antimicrobial activities were evaluated using bioluminescent bacterial strains. Compound 3 showed phototoxicity only toward the Gram-positive bacteria, whereas the cationic derivative compound 4 exhibited strong anti-bacterial activity against both Gram-positive and Gram-negative strains. These bacterial species were eradicated (>4.0 logs or 99.99% killing) at appropriate concentrations of compound 4 with 12.7 J/cm2 of red light, demonstrating compound 4 as a potent aPDT agent.
- Lin, Huajian,Chen, Jincan,Zhang, Yaxin,Ulla, Azeem,Liu, Jianyong,Lin, Fan,Jiang, Longguang,Huang, Mingdong
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p. 192 - 198
(2018/10/20)
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- VISIBLY TRANSPARENT, NEAR-INFRARED-ABSORBING AND ULTRAVIOLET-ABSORBING PHOTOVOLTAIC DEVICES
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Visibly transparent photovoltaic devices are disclosed, such as those are transparent to visible light but absorb near-infrared light and/or ultraviolet light. The photovoltaic devices make use of transparent electrodes and near-infrared or ultraviolet absorbing visibly transparent photoactive compounds, optical materials, and/or buffer materials.
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Paragraph 0350; 0351
(2019/01/07)
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- Phthalocyanine-titanate nanotubes: A promising nanocarrier detectable by optical imaging in the so-called imaging window
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TiONts-phthalocyanine nanohybrids combining an efficient optical probe and a promising nanovector have been developed in a step-by-step approach and were thoroughly characterized. Each 150 nm long TiONts-Pc bear ca. 450 Pc. Three nanohybrids were prepared including three different linkers in quest for the best stability.
- Paris,Bernhard,Boudon,Heintz,Millot,Decrau
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p. 6315 - 6322
(2015/03/05)
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- First X-ray crystallographic study of a meso-substituted tetrabenzotriazaporphyrin: Structural effect of a meso-aryl unit on 27-(2-methylphenyl)tetrabenzotriazaporphyrinato zinc example in comparison with zinc phthalocyaninate
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A recently developed synthetic procedure afforded meso-aryl substituted tetrabenzotriazaporphyrin complex, namely 27-(2-methylphenyl)tetrabenzo[b,g,l,q] [5,10,15]triazaporphyrinato zinc (2-MePhTBTAPZn, 1). The reaction also produced zinc phthalocyanine (PcZn, 2) as a byproduct. The complexes were characterized by the UV-Vis, NMR spectroscopy as well as MALDI-TOF mass spectrometry. Furthermore, they form supramolecular structures [1·DMSO]·2(DMSO) (I) and [2·DMSO]·0.65(DMSO) ·0.5(CH3OH) (II) determined by single-crystal X-ray diffraction analysis. To the best of our knowledge, I represents the first X-ray defined structure of a meso-substituted TBTAP derivative. Both structures were shown to be composed of centrosymmetric dimers, which are stabilized by the axial π-stacking intermolecular interactions. Comparison of the data for I and II indicates that the presence of the meso-aryl substituent in the TBTAP molecule results in considerable and even unexpected structural effects.
- Kalashnikov, Valery V.,Pushkarev, Victor E.,Starikova, Zoya A.,Tomilova, Larisa G.
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p. 216 - 222
(2014/03/21)
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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.
-
supporting information
p. 2797 - 2807
(2014/10/15)
-
- Magneto-optical nanomaterials: A SPIO-phthalocyanine scaffold built step-by-step towards bimodal imaging
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A SPIO-phthalocyanine nanohybrid is developed as a bimodal contrast agent for Optical and Magnetic Resonance Imaging. The organic coating was covalently attached onto SPIO in a step-by-step approach. Each coated-SPIO was thoroughly characterized. The hydrodynamic size of the SPIO-Pc is ca. 60 nm with a coverage of ca. 690 Pc/SPIO.
- Boudon, Julien,Paris, Jeremy,Bernhard, Yann,Popova, Elena,Decreau, Richard A.,Millot, Nadine
-
supporting information
p. 7394 - 7396
(2013/09/23)
-
- Lipophilic phthalocyanines for their potential interest in photodynamic therapy: Synthesis and photo-physical properties
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Several phthalocyanines with different peripheral substituents were prepared and characterized by MALDI-TOF, 1H NMR, UV-vis, fluorescence, and singlet oxygen quantum yields and retention time in HPLC normal phase. Zinc was used as a central metal ion to increase the photodynamic therapy efficiency. Phthalonitrile or 4-nitro phthalonitriles were used as starting materials. The influence of lipophilicity on the photophysical and photochemical properties was evaluated.
- Moussaron, Albert,Arnoux, Philippe,Vanderesse, Régis,Sibille, Estelle,Chaimbault, Patrick,Frochot, Céline
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p. 10116 - 10122
(2013/11/06)
-
- Synthesis, spectroscopic characterization and photophysical study of dicyanomethylene-substituted squaraine dyes
-
In this work, the synthesis and the photophysical study of novel symmetrical and unsymmetrical squaraine dyes is described. These dyes were prepared by base-catalyzed condensation reaction between 3H-indolium or benzothiazolium salts with dicyanomethylene squarate, derived from squaric acid. The photophysical behavior of the dyes was investigated using UV-Vis absorption and steady-state fluorescence in solution. Additionally, its association with albumin from bovine serum (bovine serum albumin [BSA]) was also investigated. The dyes present strong absorption in the red/infrared regions and fluorescence emission in the infrared region tailored by the electronic structure of the squaraine. Association experiments with bovine serum albumin indicate that the obtained squaraine dyes are suitable for protein detection in solution.
- Pisoni, Diego Dos Santos,Petzhold, Cesar Liberato,Abreu, Marluza Pereira De,Rodembusch, Fabiano Severo,Campo, Leandra Franciscato
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experimental part
p. 454 - 462
(2012/09/08)
-
- Substituted benzazoloporphyrazines for polymerization and surface attachment and articles formed therefrom
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The present invention provides an article of manufacture formed from a substrate and a benzazoloporphyrazine bound to the substrate. The article may take a variety of different forms and may be for example an electrochromic display, a molecular capacitor, a battery, a solar cell, or a molecular memory device. Methods of making such articles, along with compounds, methods and intermediates useful for making such benzazoloporphyrazines, are also described.
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Page/Page column 29-30
(2011/02/18)
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- Effects of the number and position of the substituents on the in vitro photodynamic activities of glucosylated zinc(ii) phthalocyanines
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A series of mono-β-, di-α- and di-β-substituted phthalonitriles which contain one or two tetraethylene-glycol-linked 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose unit(s) were prepared by typical substitution reactions. These precursors underwent self-cyc
- Liu, Jian-Yong,Lo, Pui-Chi,Fong, Wing-Ping,Ng, Dennis K. P.
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p. 1583 - 1591
(2009/06/28)
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- MICROWAVE-ASSISTED SYNTHESIS OF PERFLUOROPHTHALOCYANINE MOLECULES
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Advantageous microwave-assisted methods for synthesis of fluorinated phthalocyanines are provided. The microwave-assisted methods offer enhanced yields, substantially eliminate reaction solvents, and facilitate purification relative to conventional synthesis techniques. Typical implementation involve a reaction mixture that includes perfluoro-phthalonitrile that is reacted in a vessel with application of microwave energy for a reaction period sufficient to yield a fluorinated phthalocyanine. The fluorinated phthalocyanines synthesized according to the disclosed microwave-assisted methods have wide ranging applications, e.g., corrosion-related applications, coating-related applications, catalysis, and the production of optical and electronic materials.
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Page/Page column 6; 14
(2009/12/23)
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- Highly photocytotoxic 1,4-dipegylated zinc(ii) phthalocyanines. Effects of the chain length on the in vitro photodynamic activities
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A new series of 1,4-dipegylated zinc(ii) phthalocyanines have been synthesised and spectroscopically characterised. The derivatives ZnPc[O(CH 2CH2O)nMe]2 (n = 2, 4, ca. 12) have been prepared by mixed cyclisation of the corresponding disubstituted phthalonitriles with an excess of unsubstituted phthalonitrile in the presence of Zn(OAc)2·2H2O and 1,8-diazabicyclo[5.4.0]undec- 7-ene. The other two analogues ZnPc[O(CH2CH2O) nMe]2 (n = 6, 8) have been prepared by chain elongation reaction of ZnPc[O(CH2CH2O)4H]2. These macrocycles are highly soluble and remain non-aggregated in DMF as shown by the sharp Q-band absorption. Compared with the unsubstituted zinc(ii) phthalocyanine, these di-α-substituted analogues have a red-shifted Q band (at 689 vs. 670 nm) and exhibit a relatively weaker fluorescence emission and a higher efficiency at generating singlet oxygen. Upon illumination, these compounds are highly cytotoxic toward HT29 human colorectal carcinoma and HepG2 human hepatocarcinoma cells. The compounds with medium-length substituents are particularly potent, having IC50 values as low as 0.02 M. The high photodynamic activity of these compounds can be attributed to their high cellular uptake and low aggregation tendency in the biological media, which promote the generation of reactive oxygen species inside the cells. The effects of the chain length on the aggregation behaviour, photophysical properties, cellular uptake and in vitro photodynamic activities of this series of compounds have also been examined.
- Liu, Jian-Yong,Jiang, Xiong-Jie,Fong, Wing-Ping,Ng, Dennis K. P.
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p. 4560 - 4566
(2009/03/12)
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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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- PHTHALOCYANINE COMPOUND, PROCESS FOR PRODUCING THE SAME, AND COLORED COMPOSITION CONTAINING THE PHTHALOCYANINE COMPOUND
-
To provide a phthalocyanine compound represented by the following general formula (1), which is halogen-free and has green hue, and also has resistance to an organic solvent and an acid: in the above general formula (1), M represents a divalent to tetravalent metal atom or two hydrogen atoms, and rings A1, A2, A3 and A4 each independently represents a benzene ring or a structure represented by the above general formula (2), provided that at least one of rings A1, A2, A3 and A4 is a structure represented by the general formula (2) and, in the above general formula (2), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a tolyl group, or a xylyl group.
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Page/Page column 11-13
(2008/06/13)
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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
-
p. 213 - 219
(2008/10/09)
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- Synthesis of a new trans-A2B2 phthalocyanine motif as a building block for rodlike phthalocyanine polymers
-
Polyphthalocyanines have potential application in the development of electronic materials. One-dimensional polyphthalocyanines are accessible through monomers having a trans-A2B2 structure, but the preparation of a truly linear polyphthalocyanine is challenging because of limitations imposed by the geometry of phthalocyanines and the methodology for their synthesis. Benzimidazoporphyrazines are a known class of extra-annulated phthalocyanines. A trans-A2B2 benzimidazoporphyrazine is geometrically suitable for the preparation of rodlike polymers. A new synthesis of benzimidazoporphyrazines is presented as a stepping stone to the synthesis of trans-A2B2 benzimidazoporphyrazines.
- Youngblood, W. Justin
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p. 3345 - 3356
(2007/10/03)
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- Derivatizable phthalocyanine with single carboxyl group: Synthesis and purification
-
Phthalocyanine zinc (ZnPc) is an important class of photosensitizers. Derivatization of phthalocyanine ring with chemical functional groups provides anchor points for covalent attachment of biological targeting agents, thus increasing the selectivity of the photosensitizers. ZnPc with symmetric and multiple functional groups, e.g., tetracarboxyphthalocyanine zinc, is easy to be prepared but is unfavorable for linking targeting agents due to many reasons. On the other hand, single-substituted ZnPc, is more challenging to synthesize and, especially, to purify. Here we report the synthesis of an unsymmetrical phthalocyanine, 2-carboxyphthalocyanine zinc 1, with a single carboxylic group on phthalocyanine ring, and the design of its chromatographic purification.
- Chen, Jincan,Chen, Naisheng,Huang, Jinling,Wang, Jundong,Huang, Mingdong
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p. 313 - 315
(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)
-
- Low-temperature synthesis of phthalocyanine and its metal complexes
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Conditions for synthesizing unsubstituted phthalocyanine and its metal complexes from phthalonitrile at low temperatures (0-50°C) are optimized. Phthalocyanine and phthalocyaninates are produced under these conditions using activated Rieke metals, metals on inert substrate, sources of soluble metals in the form of unstable metal complexes, zeolites, solid-phase electrosynthesis of phthalonitrile, and UV irradiation. The use of pyrophoric metals is found to be the most efficient due to a large number of defects in their structure favoring the initial stage of phthalonitrile cyclization on a metal matrix. The suggested mechanism of formation of phthalocyanine macrocycle assumes participation of metal agglomerates occurring in activated metals. Pleiades Publishing, Inc., 2006.
- Kharisov,Ortiz Mendez,Rivera De La Rosa
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p. 617 - 631
(2008/10/09)
-
- Synthesis and photochemical characterization of a zinc phthalocyanine-zinc porphyrin heterotrimer and heterononamer
-
The synthesis of two phthalocyanine-porphyrin covalently linked heteromolecules are described. Intramolecular energy transfer is investigated and quantified in terms of the quantum yield of energy transfer and found to be highly effective in both molecules. The photophysical properties of both molecules are modified greatly by the presence of the porphyrin moieties on the phthalocyanine core. The Royal Society of Chemistry 2005.
- Zhao, Zhixin,Nyokong, Tebello,Maree, M. David
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p. 3732 - 3737
(2007/10/03)
-
- Use of elemental metals in different grade of activation for phthalocyanine preparation
-
Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Synthesis of non-substituted metal phthalocyaninates starting from phthalonitrile in various non-aqueous solvents in presence of a series of elemental metals in different grade of activation is described. Special attention is paid to phthalocyanine formation at relatively low temperatures (0-50°C). In case of use of various forms of activated and non-active nickel, it is shown that its most active form causes rapid PcNi formation at 0-25°C without addition of CH 3ONa.
- Kharisov,Coronado, C.E. Cantú,Cerda, K.P. Coronado,Méndez, U. Ortiz,Guzmán, J.A. Jacobo,Patlán, L.A. Ramírez
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p. 1269 - 1272
(2008/10/09)
-
- Synthesis and antimycotic activity of new unsymmetrical substituted zinc phthalocyanines
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The synthesis of new unsymmetrical substituted zinc phthalocyanines derivatives has been described; moreover the photodynamic activity of some compounds tested against Candida albicans has been reported.
- Cosimelli, Barbara,Roncucci, Gabrio,Dei, Donata,Fantetti, Lia,Ferroni, Fiammetta,Ricci, Micaela,Spinelli, Domenico
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p. 10025 - 10030
(2007/10/03)
-
- 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)
-
- 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)
-
- Distortion and aromatization factors on the complexing ability of tetrapyrrole macrocycles in acetonitrile
-
The kinetics of complexation between porphyrins and zinc acetate in acetonitrile was studied for the porphyrins belonging to various structural groups, including aza-, benzo-, and distorted N- and multiply substituted macrocycles. The effects of the distortion, on the one hand, and the enhanced rigidity of a macrocycle, on the other, on the complexation process were considered. The coordination of the distorted porphyrins to metal salts is facilitated because of the disturbance of the steric component of the macrocyclic effect (MCE), whereas the complexation of the rigid macrocycles is facilitated because of the activation of the electronic component of MCE.
- Berezin,Bazlova,Malkova,Andrianov
-
p. 295 - 299
(2008/10/08)
-
- Synthesis of Non-Symmetrically Benzo-Substituted Phthalocyanines and Their Electronic Spectra
-
A series of benzo-substituted phthalocyanine-Zn complexes was isolated from a mixed product of two nitriles (o-phthalonitrile and 2,3-dicyanonaphthalene) and metal salt by chromatographic techniques.The UV-Visible absorption spectra of these compounds showed a schematic variation with the mode of substitution.The D2h type complex showed strong anisotropy.
- Ikeda, Yoshihito,Konami, Hideo,Hatano, Masahiro,Mochizuki, Katsura
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p. 763 - 766
(2007/10/02)
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