İrfan Acar

Synthesis and characterization of octakis(4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy})- substituted metal-free and metallophthalocyanines

The synthesis of octakis(4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy}) metal-free (4) and metallophthalocyanines (5–8) were carried out by the cyclotetramerization of a 4,5-bis{2-[2-(1-naphthyloxy)ethoxy]ethoxy}phthalonitrile (3). Newly substituted octakisphthalocyanines showed enhanced solubility in organic solvents. The new compounds were characterized by IR, 1H-NMR, 13C-NMR, UV-Vis, and MS spectral data.

Synthesis and characterization of new metal-free and nickel(II) phthalocyanines containing hexaazadioxa macrobicyclic moieties

Novel symmetrically tetrasubstituted metal-free and metallophthalocyanines (5) and (6) which contain four hexaazadioxamacrobicycles on peripheral positions, have been synthesized. Macrobicyclic compound 3 and has been prepared by reaction of (1,3,6,9,11,14- hexaazatricyclo[12.2.1.16,9])octadecane (1) with 1,2-bis(2-iodoethoxy)-4,5-dibromobenzene (2). Compound 4 has been synthesized by reaction of compound 3 with CuCN in dry DMF. The target symmetrical phthalocyanines were separated by column chromatography and characterized by elemental analyses, 1H, 13C–NMR, IR, UV–Visible and FAB mass spectroscopies.

Fluoro functional groups substituted cobalt(II), iron(II) phthalocyanines and their catalytic properties on benzyl alcohol oxidation

In this study, phthalocyanine complexes (Co and Fe) bearing (2-{2-[3-(trifluoromethyl)phenoxy]ethoxy}ethoxy) groups at peripheral position were synthesized using the phthalonitrile derivative and characterized by IR, 1H-NMR, UV–Vis and mass spectrometry. Catalytic activity of Co(II) and Fe(II) phthalocyanines were investigated in the oxidation of benzyl alcohol with different oxygen sources. Determination of the optimal conditions for oxidation of benzyl alcohol, the catalytic reactions were carried out change the reaction temperature, oxidant/cat ratio, types of oxidants and subst./catalyst ratio.

Tetrakis (2-[2-(2-naphthyloxy)ethoxy]ethoxy) substituted metal-free and metallophthalocyanines and their aggregation behavior

Metal-free 4 and metallophthalocyanines 5, 6 and 7 substituted with four {2-[2-(2-naphthyloxy)ethoxy]ethoxy} functional groups at peripheral positions have been prepared. These new phthalocyanine compounds have been characterized by IR, UV-Vis, 1H-NMR spectroscopy, MS spectra data, and elemental analysis. The aggregation behavior of these compounds was investigated in different concentrations of chloroform. The effect of solvents on the absorption spectra was studied in various solvents.

The synthesis and characterization of new metal-free and metallo phthalocyanines substituted with four dithiatetraoxa macrocyclic moieties

New metal-free phthalocyanine (7) fused symmetrically in peripheral positions with four dithiatetraoxa macrocycles, has been synthesized by cyclotetramerization of the isoindolinediimine derivative of macrocyclic 6. Metallophthalocyanine (8) was synthesized by reaction of phthalonitrile derivative (5) with anhydrous nickel(II) chloride. The new compounds were characterized by elemental analysis, 1H and 13C-NMR, IR UV–Vis and mass spectroscopies.

Novel peripherally tetra substituted metal-free, cobalt(II), copper(II) and manganese(III) phthalocyanines bearing polyethoxy chain attached by 2,6-diphenylphenol groups: synthesis, characterization and their electrochemical studies

Metal free (6), cobalt(II) (7), copper(II) (8) and manganese(III) (9) phthalocyanines, which are tetra substituted at the peripheral positions with 2-[2-(1,1′:3′,1′′-terphenyl-2′-yloxy)ethoxy]ethoxy groups, were synthesized and characterized by IR, 1H-NMR,13C-NMR, UV–Vis and mass spectroscopy. Electrochemistry of the phthalocyanines were studied with voltammetric measurements by using cyclic voltammetry and square wave voltammetry techniques in DCM/TBAP electrolyte on a Pt working electrode. Electrochemical measurements exhibit that incorporation of redox active metal ions, CoII and MnIII, into the phthalocyanine core extends the redox capabilities of the Pc ring including the metal-based reduction couples of the metal. While MnIIIClPc showed only metal based reduction reactions, CoIIPc showed metal based and ligand based reduction reactions as expected. Cyclic and square wave voltammetric studies showed that phthalocyanines have reversible/quasireversible/irreversible redox processes, which are the main requirement for the technological usage of these compounds.

1,2,4-triazole-5(4H)-one based novel peripherally tetrasubstituted metal-free and metallophthalocyanines: Synthesis, characterization, and electrochemical and spectroelectrochemical properties

ABSTRACT In this study, the synthesis of metal-free and metallophthalocyanines containing four 4-[2-(4-methoxyphenyl)ethyl]-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one substituents at the peripheral positions were reported. The structures of compounds were characterized using IR, 1H NMR, 13C NMR, mass spectroscopies, and UV-Vis. Electrochemistry of the complexes were studied with voltammetric and in situ spectroelectrochemical measurements in different electrolytic systems. MPcs having redox inactive metal centers (H+, Zn+2, Cu+2, and Ni+2) just illustrated similar Pc-based electron transfer reactions. Due to the different effective nuclear charge of the ions in the core of Pc ring, small potential shifts and reversibility differences were observed between the redox processes of these complexes. MPcs having redox-active metal centers (Co+2 and TiO+2) gave metal-based electron transfers in addition to Pc-based processes. Electrolyte type of the measurement system significantly influenced oxidation behaviors of CoPc due to the coordination of polar coordinating solvent molecules to the oxidized CoIII center of CoPc. Spectra and color of the electrogenerated MPc species were determined with in situ spectroelectrochemical measurements.

Synthesis and electrochemistry of new octa-substituted metal-free and metallophthalocyanines

The synthesis and characterization of metal-free (H2-Pc) and metal-containing (Zn, Co, and Cu) derivatives of a symmetrically octa-substituted phthalocyanine derived from 4,5-bis[2-(phenylthio)ethoxy]phthalonitrile were carried out by microwave irradiation. The electrochemical properties of the metal-free phthalocyanine 4 and metallophthalocyanine complexes 5 and 6 were investigated by cyclic voltammetry and differential pulse voltammetry. We have previously investigated the electrochemical properties of the tetra substituted 2-(phenylthio)ethoxy phthalocyanines. The reduction potential of the octa-substituted metal-free phthalocyanine shifted to more negative potential as a result of the electron donating of the 2-(phenylthio)ethoxy groups on the periphery compared to those of tetra substituted. The H2Pc and ZnPc demonstrated ligand-based electron transfer processes, while CoPc complex has a metal-based reduction process. Similar aggregation behavior was observed for octa-substituted phthalocyanines. The compounds were characterized using IR, 1H NMR, 13C NMR, elemental analysis, and MS spectral data. Graphical Abstract

Synthesis and investigation of spectroelectrochemical properties of peripherally tetra-substituted phthalocyanine bearing 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol and its metallo compounds

In this study, the new compounds; 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol 3 was prepared by the reaction of 4-(3-hydroxypropyl)phenol 1 with 1-(bromomethyl)-3-(trifluoromethyl)benzene 2 and 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] phthalonitrile 5 was synthesized by the reaction of 4-nitrophthalonitrile 4 with 3-(4-{[3-(trifluoromethyl)benzyl]oxy}phenyl)propan-1-ol 3. Novel peripherally tetra substituted H2Pc 6, Co(II) 7, Cu(II) 8, Ni(II) 9 and Fe(II) 10 phthalocyanines, which have peripheral positions with 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups, were synthesized and all of the new compounds characterized by IR, 1H NMR, 13C NMR, UV–Vis, mass spectroscopies and elemental analysis. The electrochemical and spectroelectrochemical investigation of the phthalocyanines carrying 4-[3-(4-{[3 (trifluoromethyl)benzyl]oxy}phenyl)propoxy] groups were studied using various electrochemical techniques in DMF on a glassy carbon electrode. Cyclic voltammetry and square wave voltammetry studies show that the complexes have either metal based or ligand-based diffusion controlled electron transfer properties. To shed more light on the electron-transfer steps of the complexes and assignments of the redox couples were carried out by spectroelectrochemical measurements. The color changes during spectral changes of redox species were recorded with in situ electrocolorimetric measurements. The electrochemical and in situ UV–Vis spectral change of complexes indicated their applicability in the fields of the electrochemical technologies.