14320-04-8Relevant articles and documents
The solid phase, room-temperature synthesis of metal-free and metallophthalocyanines, particularly of 2,3,9,10,16,17,23,24-octacyanophthalocyanines
Nemykin, Victor N.,Kobayashi, Nagao,Mytsyk, Vladislav M.,Volkov, Sergey V.
, p. 546 - 547 (2000)
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.
Novel synthesis of phthalocyanines from phthalonitriles under mild conditions
Uchida, Hitoshi,Tanaka, Hirokazu,Yoshiyama, Hideyuki,Reddy, Paidi Yella,Nakamura, Shuichi,Toru, Takeshi
, p. 1649 - 1652 (2002)
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.
Electrochemistry of metal phthalocyanines in organic solvents at variable pressure
Yu, Bazhang,Lever,Swaddle, Thomas W.
, p. 4496 - 4504 (2004)
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).
Zn phthalocyanine/carbon nitride heterojunction for visible light photoelectrocatalytic conversion of CO2 to methanol
Zheng, Jingui,Li, Xiaojie,Qin, Yuhu,Zhang, Shuqin,Sun, Mingsheng,Duan, Xiaoguang,Sun, Hongqi,Li, Peiqiang,Wang, Shaobin
, p. 214 - 223 (2019)
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.
Chemically reversible reactions of hydrogen sulfide with metal phthalocyanines
Hartle, Matthew D.,Sommer, Samantha K.,Dietrich, Stephen R.,Pluth, Michael D.
, p. 7800 - 7802 (2014)
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
Phthalocyanization of Cadmium Sulfide and Zinc Oxide. Effects on the Photochemistry in Aqueous Dispersion
Harbour, John R.,Dietelbach, Bonita,Duff, James
, p. 5456 - 5460 (1983)
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.
Green synthesis and characterization of crystalline zinc phthalocyanine and cobalt phthalocyanine prisms by a simple solvothermal route
Li, Dapeng,Ge, Suxiang,Yuan, Tianci,Gong, Jingjing,Huang, Baojun,Tie, Weiwei,He, Weiwei
, p. 2749 - 2758 (2018)
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.
Coordination properties of diethylenetriamine in relation to zinc phthalocyanine
Janczak, Jan
, (2020)
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.
Syntheses and Characterization of Bromo- and Chloro(phthalocyaninato)bismuth(III) Complexes
Isago, Hiroaki,Kagaya, Yutaka
, p. 383 - 389 (1994)
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.
Comparative study of beryllium, magnesium and zinc phthalocyanine complexes with 4-picoline
Kubiak,Janczak,?led?,Bukowska
, p. 4179 - 4186 (2007)
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.
Fluorinated phthalocyanines as molecular semiconductor thin films
Brinkmann,Kelting,Makarov,Tsaryova,Schnurpfeil,Woehrle,Schlettwein
, p. 409 - 420 (2008)
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.
Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
Hosseini-Sarvari, Mona,Koohgard, Mehdi
, p. 5905 - 5911 (2021/07/12)
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.
