Ball-type Phthalocyanines Research Articles

Novel Ball-Type Phthalocyanines with Eight Benzotriazole Groups: Synthesis, Computational DFT Studies, and Supercapacitor Properties

Novel four MBTOB-bridged ball-type metallophthalocyanines were obtained from 4,4′-((methylenebis(6-(2H-benzo[d][1, 2, 3]triazol-2-yl)−4-(2,4,4-trimethylpentan-2-yl)−2, 1-phenylene))bis(oxy))diphthalonitrile by means of transition metal (II) acetate salts in 2-dimethylaminoethanol. The new starting bisphthalonitrile compound was accomplished from 2,2′-methylenebis[6-(benzotriazol-2-yl)−4-tert-octylphenol] and 4-nitrophthalonitrile in dimethylformamide under the catalysis of potassium carbonate at 50 °C. The structural characterization of the compounds was accomplished by infrared, proton-nuclear magnetic resonance, matrix-assisted laser desorption/ionisation time-of-flight mass, and ultraviolet–visible spectroscopic methods. The supercapacitor performances of the electrodes were examined by cyclic voltammetry, galvanostatic charge discharge, and electrochemical impedance spectroscopy analyses. The specific capacitances obtained from the GCD measurements were calculated as 320.4 ± 15.1 F g−1 for ball-type zinc (II) phthalocyanine in three electrode systems. The highest specific capacitance value was found in the electrode containing ball-type nickel (II) phthalocyanine as 929.8 ± 32.8 F g−1 at a scan rate of 100 mV s−1. In symmetric supercapacitor measurements, the capacitance retention value was 100.7% after 5000 cycles.

Synthesis and characterization of novel HMPM bridged ball-type metallophthalocyanines, and their DFT studies and electrochemical performance as supercapacitor electrodes

Novel 4, 4′-((((2-(3, 4-dicyanophenoxy)-5-methyl-1, 3-phenylene) bis (methylene)) bis (4-methyl-3, 1-phenylene)) bis (oxy)) -bridged ball-type phthalocyanines were achieved from 4, 4′-((((2-(3, 4-dicyanophenoxy)-5-methyl-1, 3-phenylene) bis (methylene)) bis (4-methyl-3, 1-phenylene)) bis (oxy)) diphthalonitrile through appropriate transition metal (II) acetate salts in 2-dimethylaminoethanol. The new tris-phthalonitrile precursor was achieved from 3,3′-((2-hydroxy-5-methyl-1,3-phenylene) bis (methylene)) bis (4-methylphenol), and 4-nitrophthalonitrile with the presence of catalyst potassium carbonate in dimethylformamide at 50○C. The structural verification of the compounds was accomplished by proton-nuclear magnetic resonance, matrix-assisted laser desorption/ionization time-of-flight mass, infrared, and ultraviolet–visible spectroscopic methods.The BTCuPc electrode material exhibited a specific capacitance of 265 F.g−1 at a scan rate of 5 mV.s−1 in 3.0 M KCl aqueous electrolyte. In addition, a wide operating potential range (1.5 V) was achieved in the aqueous electrolyte.

Ball-type phthalocyanines and reduced graphene oxide nanoparticles as separate and combined corrosion inhibitors of aluminium in HCl

Corrosion inhibition performances and adsorption behaviour at the aluminum-HCl solution interface were investigated for reduced graphene oxide nanosheets (rGONS), tetrakis-[4,4′-((4-(benzo[d]thiazol-2-yl)-1,2-bis(phenoxy)] (diphthalocyaninato gallium (III) chloride) (2) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium(III) chloride) (1). Corrosion inhibition effects of rGONS, 1 and 2 were evaluated alone and in combination in 1.0 M hydrochloric acid solution using electrochemical techniques. The mechanism of aluminum corrosion inhibition revealed predominantly anodic character for rGONS and predominantly cathodic character for 1, 2, and conjugates with rGONS . The polarization technique gave inhibition efficiency values of 96.5% and 96.9% respectively for 1 and 2, which increased in the presence of rGONS to 97.4% and 98.1%, respectively, for the highest concentrations of 1 and 2. Scanning electron microscopy revealed effective metal surface protection by the inhibitors by formation of protective films.

In vitro antiproliferative effect of four ball-type phthalocyanines linked by t-butylcatechol and high singlet oxygen production

Four ball-type phthalocyanines (H2Pc, MgPc, CoPc, and ZnPc) containing 4-tert-butylcatechol substituents at alpha-positions were synthesized from 3,3′-(4-tert-butyl-1,2-phenylene)bis(oxy)diphthalonitrile. The structures were elucidated by elemental analysis and ultraviolet-visible, Fourier-transform infrared, proton nuclear magnetic resonance, and Maldi-Tof mass spectroscopies. The photophysicochemical properties of H2Pc, MgPc, and ZnPc were investigated in dimethylsulphoxide. The fluorescence quantum yields (ΦF), triplet state quantum yields (ΦT), and singlet oxygen quantum yields (ΦΔ) with respect to H2Pc, MgPc and ZnPc were experimentally obtained. Furthermore, the degradation quantum yield (Φd) was evaluated for all complexes. Finally, the magnetic circular dichroism spectra of the four Pcs were obtained. Among these ball-type phthalocyanines, MgPc had the highest triplet lifetime and ZnPc had the highest singlet oxygen quantum yield. Moreover, the in vitro antiproliferative effect of ball-type phthalocyanines (H2Pc, MgPc, CoPc, and ZnPc) was evaluated on MCF-7 cell line originated from luminal A breast cancer and MDA-MB-231 cell line originated from triple negative breast cancer. For this purpose, cell viability MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay was used. For all compounds, 0.2, 0.4, 0.8, 1.6, 3.2, 6.4, 12.8, 25.6, 51.2, 102.4 µM concentrations were applied to both cell lines. There was a significant decrease in cell viability for MCF-7 and MDA-MB-231 cells (p < 0.05).

Photo-physico-chemical properties of 1,3-benzenediol-substituted face-to-face phthalocyanines

Here, we report the synthesis of new ball-type phthalocyanines that are symmetrically substituted with Mg–Mg, Zn–Zn, and Co–Co centers and contain four 1, 3-benzenediol substituents at the beta positions. The structures and photophysical properties, including the fluorescence quantum yield, triplet quantum yield, and photochemical properties with singlet oxygen quantum yield, of these compounds were investigated. Moreover, the applicability of these molecules as photosynthesizers in cancer nanomedicines is discussed. Furthermore, the photodegradation quantum yield of the complexes with the inclusion of Co binuclear phthalocyanine was examined, and their fluorescence and triplet lifetimes were studied in dimethyl sulfoxide. The obtained Uv–Vis spectra exhibited unexpected results; for instance, H2Pc exhibited a broad and peculiar Q band with D4h symmetry. Moreover, H2Pc was found to have a triplet lifetime of 460 µs whereas ZnPc had a higher triplet lifetime of 1100 µs.

Synthesis, photophysics, and photochemistry of ball-type phthalocyanines

Phthalocyanines (Pcs) have numerous potential applications, including use as photosensitizers for photodynamic cancer therapy. These applications depend on specific photodynamic properties; therefore, new Pc compounds with unique and well characterized properties are in constant demand. In this study, four novel ball-type Pc compounds were synthesized with 1,2-benzenediol as a substituent, including one non-metal complex (H4Pc2) and three metal-containing complexes (Mg2Pc2, Co2Pc2, and Zn2Pc2). The structures of the synthesized compounds were characterized using common spectroscopic methods. Quantum yields for fluorescence (ΦF), triplet state (ΦT), singlet oxygen (ΦΔ), and photodegradation (Φd) were measured except Co2Pc2 in dimethylsulfoxide. All the three compounds exhibited low fluorescence quantum yield, high triplet quantum yield, and good stability in organic solvent, suggesting acceptable photostability. Complexes with H4Pc2 and Mg2Pc2 demonstrated differences in the Q band in their Uv–Vis spectra. Singlet oxygen quantum yield was 0.35 for Zn2Pc2. Fluorescence lifetimes (τF) for the complexes ranged from 6.67 to 2.95 ns, while triplet state lifetimes (τT) ranged from 50 to 440 μs. This novel group of Pcs possesses properties suitable for photodynamic therapy, particularly ZnPc.

Mini-Review: “Ball-Type Phthalocyanines”: Similarities and Differences from Mono Phthalocyanines

Ball-type phthalocyanines are recently synthesized binuclear derivatives of the widely known phthalocyanine molecule. In the ball-type Pc molecule, two cofacially arranged Pc rings have four bridged substituents on the peripheral positions of benzenes. Due to their cofacially arranged phthalocyanine rings and, strong intramolecular and intermolecular interactions, ball-type phthalocyanines have different properties than their parent molecule and these structures have many potential application areas. This review describes three different synthesis methods of ball-type phthalocyanines; synthesis in the solvent, synthesis in solid, and synthesis under microwave irradiation. The synthesis that occurs in the shortest time with the highest yield is the synthesis in the solid phase. General differences between a ball-type phthalocyanine and a monophthalocyanine, such as differences in electronic spectra and effects of cofacial arrangement and central metal atoms, are also discussed. The shape of the Q-bands indicates the differences in electronic spectra. In ball-type Pcs, the Q-bands are broad and have poor resolution. Some potential applications, such as gas sensors, NLO devices, potential usage in photodynamic therapy and artificial photosynthesis of ball-type phthalocyanines are also mentioned. Ball-type Pcs can be used as a sensor for gases such as; CO2, CO, SO2, VOC. A novel water-soluble ball-type Pc may have potential application in PDT. Finally, we consider future prospects of these molecules.

Enhanced nonlinear optical response of benzothiazole substituted ball-type phthalocyanines in the presence of metallic nanoparticles

The synthesis of zinc-zinc, gallium-gallium and indium-indium ball-type phthalocyanines (complexes 4, 5 and 6) and the surface assembly of the complexes onto metallic gold and silver nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical dynamics were investigated. Decreases in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to complexes 4, 5 and 6 alone were observed. The mechanism of strong reverse saturable absorption observed was found to be predominantly dependent on excited state absorption. The optical limiting thresholds range from 0.09 to 0.19 J/cm2. Enhanced triplet parameters and nonlinear optical responses were found when the complexes were conjugated to metallic nanoparticles.

Synthesis, characterization and OFET property of four diaminouracil bridged novel ball-type phthalocyanines

New ball-type metallobisphthalocyanines 2 (Co[Formula: see text]Pc[Formula: see text] and 3(Zn[Formula: see text]Pc[Formula: see text] were synthesized from the corresponding 4,4[Formula: see text]-[(5,6-diaminopyrimidine-2,4-diyl)bis(oxy)] diphytalonitril 1, which can be obtained by a nucleophilic displacement reaction of 4-nitrophthalonitrile with 5,6-diaminouracil sulfate. Characterization of novel compounds was performed by UV-vis, FT-IR, [Formula: see text]H-NMR, MALDI-TOF mass spectroscopy and elemental analysis. Organic field effect transistor devices (OFETs) with top gate structure were fabricated using these novel compounds as the active material. The devices were characterized by means of their output and transfer characteristics, and it was found that these OFET devices exhibit [Formula: see text]-type behavior. When compared with the 2-based device, the OFET with 3 showed higher field effect mobility and larger on/of current ratio.

Photophysical and strong optical limiting properties of ball-type phthalocyanines dimers and their monomeric analogues

Abstract The nonlinear optical behaviors of ball-type phthalocyanine complexes: 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl))bis(phthalocyaninato zinc (II)] (5), 1′,11,’15′,25′-tetrakis-[4,4′-((4-formyl-1,2-bisphenoxyl) bis(phthalocyaninato gallium (III) chloride)] (6), and 1′, 11,’15′,25′-tetrakis-4,4′-((4-formyl-1,2-phenoxyl)bis(phthalocyaninato indium (III) chloride)] (7) and the corresponding monomeric derivatives 8–10 were investigated using nanosecond pulse open aperture Z-scan technique at 532 nm. The nonlinear response showed strong reverse saturable absorption for all the complexes both in solution and when embedded in polymer matrix. The dimeric complexes showed better optical limiting properties compared to the monomeric derivatives. The βeff values for the dimeric complexes 5–7 were found to be 48.5, 55.2, and 60.1 cm/GW for 5, 6A, and 7 respectively, higher than the corresponding monomeric derivatives 8–10. Enhanced optical limiting properties were observed when the complexes were formulated in thin films. The second order hyperpolarizability values were in order of 10−28–10−26 esu in solution and 10−27–10−26 in films.

Synthesis, photophysical and nonlinear optical properties of a series of ball-type phthalocyanines in solution and thin films

Ball-type phthalocyanines containing heavy central metals show enhanced nonlinear optical behaviour in solution or when embedded in polymer thin films. Time dependent density functional theory (TD-DFT) calculations were used to explain the spectra.

Novel 4,4′-{(diphenylmethylene) bis(4,1-phenylene)bis(oxy)}-bridged ball-type phthalocyanines: Electrochemical, electrocatalytic oxygen reducing and heavy metals ions sensing properties

Novel 4,4′-{(diphenylmethylene)bis(4,1-phenylene)bis(oxy)} bridged ball-type metal-free, zinc(II), cobalt(II) and iron(II) ball-type metallophthalocyanines were achieved by the reaction of the bisphthalonitrile derivative in 2-dimetylaminoethanol. The isolation of the metal-free and metallophthalocyanines were carried out by both planar and column chromatography and also by hot soxhalet extraction. Their structures have been characterized by infrared, ultraviolet-visible,1H nuclear magnetic resonance and matrix assisted laser desorption/ionization mass spectroscopies. The redox characters of the ball-type metallophthalocyanines have been investigated by cyclic voltammetry, square wave voltammetry, controlled potential coulometry and spectroelectrochemistry in nonaqueous media. The investigation suggested that the ball-type complexes form ring-based and/or metal-based mixed-valence species as a result of the remarkable interaction between the two Pc rings and/or metal centers. Furthermore, these species were found to be stable as evidenced by the splitting of the relevant redox processes. The electrocatalytic oxygen reducing performances of the dinuclear ball-type complexes were also studied. The compound involving Fe(II) centers at the phthalocyanine cores displayed higher catalytic performance towards oxygen reduction than those of other ones. By using these compounds as sensing materials, a flow type quartz crystal microbalance sensor was developed for the detection of small concentrations of heavy metal ions. A cadmium ion sensitivity of 2.85 × 104Hz/mg.L[Formula: see text] was observed with ball-type iron(II) phthalocyanine coated quartz crystal microbalance sensor. Detection of other metal ions including Fe[Formula: see text], Zn[Formula: see text], Ag[Formula: see text] and Sn[Formula: see text] were also performed. The results indicated that 1– 4 functionalized quartz crystal microbalance sensors can be used for the detection of heavy metal ions in aqueous solution. Partition coefficients obtained from the linear response regimes of the calibration curves are in the 8.6 × 104–5.4 × 105range. Results show that the minor structural difference between metal free and metallophthalocyanine poses significant impact on metal ion partitioning.

Partition coefficient-Lewis basicity correlation in four dioxycyclobutenedion-bridged novel ball-type phthalocyanines

The novel ball-type bis-metallo [Zn(II), Co(II) and Cu(II)] phthalocyanines were synthesized from 4,4′-(3,4-dioxocyclobut-1-ene-1,2-diyl)-bis(oxy)] diphthalonitrile, which can be obtained by the reaction of 4-nitrophthalonitrile with 3,4-dihydroxy-3cyclobuten-1,2-dione. The novel ball-type phthalocyanines with cyclobutene unit were characterized by elemental analysis, UV–vis, FT-IR, 1H NMR, and MALDI-TOF mass spectroscopy. The response and recovery behaviours of the films to different analytes, which span a broad range of Lewis base, were investigated by utilizing an AT-cut quartz crystal resonator. Frequency changes during transient exposures to these vapours were rapid and reversible. The sensing behaviour of the films for a broad range of Lewis bases and the correlation between the partition coefficients and Lewis base enthalpies were investigated. Partition coefficients obtained from the linear response regimes of the calibration curves were in the 800–22,000 range. Results show that partition coefficients may be correlated exponentially with binding enthalpy.

Synthesis, characterization and gas sensing properties of novel homo and hetero dinuclear ball-type phthalocyanines.

New ball-type homodinuclear Co(ii)-Co(ii) phthalocyanine () and ball-type heterodinuclear Co(ii)-Fe(ii) phthalocyanine () were synthesized from the corresponding [2,10,16,24-tetrakis{4,4'-cyclohexylidenebis(2-cyclohexyphenoxyphthalonitrile)}phthalocyaninatocobalt(ii)] (). The novel compounds have been characterized by elemental analysis, IR, UV-Vis and MALDI-TOF mass spectroscopy. Gas sensing capability of the spin coated film of and were studied using amperometric technique at various temperatures. For a better understanding of the interaction of and films with organic compounds, two different groups of compounds (aromatics and alcohols) were selected as test analytes. It was observed that the operating temperature had a considerable effect on the gas sensing performance of the sensors investigated. The experimental results show that film offers a promising perspective as a sensing material for the detection of relatively low aromatic vapours even at room temperature. This suggests that aromatics might be distinguished from alcohols. The obtained data were analysed using two different adsorption kinetic models: the pseudo first order equation and Elovich equation to determine the best fit equation for the adsorption of toluene vapor onto and films. The first-order equation was the best of the various kinetic models studied to describe the adsorption kinetic of toluene on Pc films at higher concentrations, as evidenced by the highest correlation coefficients. In addition, it was observed that Elovich equation generates a straight line that best fit to the data of adsorption of lower concentrations of toluene.

History, development, and a new concept of phthalocyanines in Turkey

This paper reviews the history of phthalocyanines in Turkey. Phthalocyanines are chemical compounds that were accidently discovered nearly a century ago. The relevant research and articles have grown dramatically in Turkey since our first paper on them containing four [15]crown[5] published in 1986. The ball-type phthalocyanines were produced and published as a new concept in phthalocyanine chemistry for the first time by our group in Turkey in 2006. Unfortunately, with the exception of our work on this subject, almost no papers have been published in Turkey or in other countries since then. We strongly urge scientists to consider working on this new type of phthalocyanine, which shows interesting development potential in electrical, electrochemical, and photovoltaic applications as well as oxygen reduction for fuel cells.

Electrochemical and electrical properties of novel mono and ball-type phthalocyanines

New mononuclear Co(II) phthalocyanine 3 and ball-type homobinuclear Cu(II)–Cu(II) and Zn(II)–Zn(II) phthalocyanines, 4 and 5 respectively, were synthesized using the corresponding metal salts and the 4,4′-(methane-5-methyl-3-(1-methylcyclohexyl)-2,2′-phenoxy)diphthalonitrile ligand 2, which was prepared from the reaction of 4-nitrophthalonitrile with bis[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]methane (1). The novel compounds 3–5 have been characterized using their elemental analysis data and UV–Vis, IR, 1H NMR and MALDI-TOF mass spectra. The redox properties of the complexes were investigated by cyclic voltammetry in a non-aqueous medium. The electrochemical measurements showed that complex 5 forms a mixed-valence reduction species, due to the strong intramolecular interactions between the two phthalocyanine rings. Complex 4 displayed Pc ring-based redox signals with very high peak currents, which were attributed to the adsorption of the complex on the working electrode. Dc and ac electrical properties of films of 3, 4 and 5 were also investigated as a function of temperature (295–523K) and frequency (40–105Hz). From the dc conductivity measurements, activation energy values of the films were found, being 0.70, 0.66 and 0.68eV for films of 3, 4 and 5, respectively. From impedance spectroscopy measurements, it was observed that the bulk resistance decreases with increasing temperature, indicating semiconductor properties.

Synthesis, interface (Au/M2Pc2/p-Si), electrochemical and electrocatalytic properties of novel ball-type phthalocyanines

The phthalodinitrile derivative (3) was prepared by the reaction of 4,4'-(octahydro-4,7-methano-5H-inden-5-ylidene)bisphenol (1) and 4-nitrophthalonitrile (2) with dry DMF as the solvent in the presence of the base K(2)CO(3) by the method of nucleophilic substitution of an activated nitro group in an aromatic ring. The template reaction of 3 with the corresponding metal salts gave the novel bi-nuclear ball-type metallophthalocyanines, MPcs {M = Co (4), Cu (5), Zn (6)}. Newly synthesized compounds were characterized by elemental analysis, UV-vis, FT-IR (ATR), MALDI-TOF mass and (1)H-NMR spectroscopy techniques. The electronic spectra exhibit an intense π→π* transition of characteristic Q and B bands of the Pc core. The dielectric properties and interface between the spin coated films of 4-6 and a p-type silicon substrate have been studied by fabricating metal-insulator-semiconductor capacitors. The results indicated that the frequency dependence of the dielectric permittivity, ε'(ω), exhibits non-Debye type relaxation for all the temperatures investigated. The ac conductivity results indicated that the conduction mechanism can be explained by a hopping model at low temperatures (<430 K) and a free band conduction mechanism at high temperatures (≥430 K). The density of interface state calculations on these novel compounds showed that the combination of Au/4/p-Si is a promising structure with a high dielectric constant and a low interface trap density suitable for metal-oxide-semiconductor devices. The electrochemical properties of the Pc complexes were examined by cyclic voltammetry, differential voltammetry and controlled potential coulometry on platinum in non-aqueous media. The complexes showed ring-based and/or metal-based mixed-valence behaviours as a result of the remarkable interaction between the two Pc rings and/or metal centres. The mixed-valence splitting values for the complexes suggested that the mixed valence species are considerably stable. The Vulcan XC-72(VC)/Nafion(Nf)/4 modified glassy carbon electrode showed much a higher catalytic performance towards oxygen reduction than those of VC/Nf/5 and VC/Nf/6 modified ones.

Photovoltaic and electrocatalytic properties of novel ball-type phthalocyanines bridged with four dicumarol

The new ball-type metallo bisphthalocyanines (Co(2)Pc(2) and Zn(2)Pc(2)) were synthesized from the corresponding [4,4'-bis(dicoumaroylphthalonitrile)] which can be obtained from the reaction of 3,3'-methylenebis(4-hydroxy-2H-chromen-2-one) and 4-nitrophthalonitrile. The structures of the newly synthesized compounds have been confirmed and characterized by elemental analysis, UV/Vis, IR and (1)H NMR spectroscopies and MALDI-TOF mass spectrometry. Solar cells of the configuration ITO/Co(2)Pc(2)/C60/Al and ITO/Zn(2)Pc(2)/C60/Al were fabricated. The effect of the thickness of the active Pc layer--the thickness of the Pc layer was varied from 15 to 80 nm--on solar cells parameters has been investigated. A nearly thickness independent open circuit voltage was observed in both structures. The maximum photovoltaic conversion efficiency, short circuit current and fill factor were observed in ITO/Zn(2)Pc(2)/C60/Al cell with 80 nm Pc layer to be 0.255%, 1 mA cm(-2) and 0.38, respectively. The redox properties of the ball-type complexes were investigated by cyclic voltammetry, controlled-potential coulometry and in situ spectroelectrochemistry in DMSO-TBAP. The electrochemical measurements showed that the complexes form ring-based and/or metal-based mixed-valence species, due to the remarkable intramolecular interactions between the two metal phthalocyanine units. The Vulcan XC-72(VC)/Nafion(Nf)/Co(2)Pc(2) modified glassy carbon electrode showed much higher catalytic performance towards oxygen reduction, compared to the VC/Nf/Zn(2)Pc(2) modified one. It was found that the VC/Nf/Co(2)Pc(2) catalyst is nearly insensitive to the presence of methanol. In the presence of 1 M methanol in the electrolyte, the catalytic performance of the Co(2)Pc(2)-based catalyst in oxygen reduction was much better than that of the Pt-based one. Thus, it was shown that the VC/Nf/Co(2)Pc(2) catalyst can be a good alternative to VC/Nf/Pt as a cathode catalyst in direct methanol fuel cells.

Novel homo- and heterobinuclear ball-type phthalocyanines: synthesis and electrochemical, electrical, EPR and MCD spectral properties

The mononuclear Fe(II) phthalocyanine 2 and ball-type homobinuclear Fe(II)-Fe(II) and Cu(II)-Cu(II) phthalocyanines, 3 and 4 respectively, were synthesized from the corresponding 4,4'-[1,1'-methylenebis-(naphthalene-2,1-diyl)]bis(oxy)diphthalonitrile 1, and then ball-type heterobinuclear Fe(II)-Cu(II) phthalocyanine 5 was synthesized from 2. The novel compounds 4 and 5 have been characterized by elemental analysis, UV/vis, IR and MALDI-TOF mass spectroscopies. Electron paramagnetic resonance and magnetic circular dichroism measurements of 3, 4 and 5 were also examined. The voltammetric measurements of the complexes showed the formation of various electrochemically stable ligand- and metal-based mixed-valence species, due to the intramolecular interactions between the two MPc units, especially in ball-type binuclear iron(II) phthalocyanine. Impedance spectroscopy and d.c. conductivity measurements of 4 and 5 were performed as a function of temperature (295-523 K) and frequency (40-10(5) Hz). While room temperature impedance spectra consist of a curved line, a transformation into a full semicircle with increasing temperature was observed for both compounds.

Synthesis, characterization, electrochemical and CO 2 sensing properties of novel mono and ball-type phthalocyanines with four phenolphthalein units

The novel mono metallo [Zn(II) 4 and Co(II) 5] and ball-type or cofacial bis-metallo [Zn(II) 6 and Co(II) 7] phthalocyanines have been synthesized from 3, which can be obtained by the reaction of 4-nitrophthalonitrile 1 with 3,3-bis(4-hydroxy-phenyl)isobenzofuran-1(3 H)-one 2 (phenolphthalein). The phthalocyanines have been characterized by elemental analysis, UV–vis, IR, 1H NMR, and mass spectroscopy. The redox behavior of the complexes was investigated by cyclic voltammetry and controlled-potential coulometry. The electrochemical measurements suggested the formation of mixed-valent species during the redox processes of bis-metallophthalocyanines 6 and 7, as a result of the intramolecular interactions between two cofacial Pc units. The effect of temperature on the CO 2 sensing properties of a spin-coated thin film of 7 was also investigated.