Novel alpha-7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin substituted metal-free, Co(II) and Zn(II) phthalocyanines: Photochemistry, photophysics, conductance and electrochemistry

Abstract Novel alpha-substituted metal-free, Co(II) and Zn(II) phthalocyanines, bearing four 7-oxy-4-(4-methoxyphenyl)-8-methylcoumarin moieties were synthesized. The compounds were characterized by elemental analysis, IR, UV– vis, 1 H NMR, 13 C NMR and MALDI-TOF mass spectroscopies. The Zn(II) phthalocyanine compound showed J-type aggregation in non-coordinating solvents. The photophysical and photochemical properties of these compounds were described in different solvents. Direct current conductivity measurements of the films of Co(II) and Zn(II) phthalocyanines as a function of temperature showed that these compounds are semiconductors with the activation energies within the range of 0.40–0.84 eV. The variation of alternating current conductivity of the films with frequency was found to be represented by the function σ AC  = A ω s . The results indicated that charge transport mechanism of the films can be explained by hopping. The redox properties of the compounds were also examined in dimethylsulfoxide and dichloromethane by voltammetry and in situ spectroelectrochemistry. The compounds displayed metal and/or phthalocyanine ring-based reduction and oxidation processes. The electrochemistry of a phthalocyanine compound forming a J-aggregated species has been investigated. It was found that some redox couples of the Zn(II) compound in dichloromethane is split due to the equilibrium between its aggregated and non-aggregated species.

[1]  R. D. George,et al.  Synthesis of 3-nitrophthalonitrile and tetra-α-substituted phthalocyanines , 1995 .

[2]  A. Altındal,et al.  Synthesis, characterization, conduction and gas sensing properties of novel multinuclear metallo phthalocyanines (Zn, Co) with alkylthio substituents , 2006 .

[3]  B. Salih,et al.  Synthesis, characterization, and electrochemical, and electrical measurements of novel 4,4′-isopropylidendioxydiphenyl bridged bis and cofacial bis-metallophthalocyanines (Zn, Co) , 2008 .

[4]  K. Law.  Effect of dye aggregation on the photogeneration efficiency of organic photoconductors , 1988 .

[5]  A. Koca,et al.  Voltammetric, spectroelectrochemical, and electrocatalytic properties of thiol-derivatized phthalocyanines , 2008 .

[6]  A. Koca,et al.  Electrochemical and spectroelectrochemical characterization of the phthalocyanines with pentafluorobenzyloxy substituents , 2007 .

[7]  Dennis K. P. Ng,et al.  Synthesis and photophysical properties of nonaggregated phthalocyanines bearing dendritic substituents , 1999 .

[8]  D. Schlettwein,et al.  Spectroelectrochemical investigations on the reduction of thin films of hexadecafluorophthalocyaninatozinc (F16PcZn) , 1999 .

[9]  Yasin Arslanoğlu,et al.  Electrochemistry, spectroelectrochemistry and electrochemical polymerization of titanylphthalocyanines , 2007 .

[10]  A. Koca,et al.  Synthesis, electrochemical and spectroelectrochemical properties of highly soluble tetra substituted phthalocyanines with [4-(thiophen-3-yl)-phenoxy] , 2011 .

[11]  A. Özkaya,et al.  Synthesis, characterization and some properties of novel bis (pentafluorophenyl )methoxyl substituted metal free and metallophthalocyanines , 2006 .

[12]  Fushi Zhang,et al.  Photoresponsive J-aggregation behavior of a novel azobenzene-phthalocyanine dyad and its third-order optical nonlinearity. , 2008, The journal of physical chemistry. B.

[13]  A. Koca,et al.  Selective metal sensor phthalocyanines bearing non-peripheral functionalities: Synthesis, spectroscopy, electrochemistry and spectroelectrochemistry , 2009 .

[14]  Hyun-jin Lee,et al.  Enhanced Acidity, Photophysical Properties and Liposome Binding of Perfluoroalkylated Phthalocyanines Lacking C-H Bonds , 2006, Photochemistry and photobiology.

[15]  J. Muto,et al.  Electrical and structural properties of ortho-chloranil doped zinc phthalocyanine films , 1991 .

[16]  M. Sülü,et al.  Synthesis, characterization and electrical and CO2 sensing properties of triazine containing three dendritic phthalocyanine , 2005 .

[17]  P. A. Harris,et al.  A novel and facile synthesis of 7,8-diacylcoumarins , 2007 .

[18]  B. Salih,et al.  Synthesis, Characterization, and Electrochemical and Electrical Properties of Novel Pentaerythritol-Bridged Cofacial Bismetallophthalocyanines and Their Water-Soluble Derivatives , 2007 .

[19]  A. Koca,et al.  Synthesis, electrochemical, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of non-peripheral tetrasubstituted metal-free and metallophthalocyanines , 2011 .

[20]  Ghosh,et al.  Frequency-dependent conductivity in bismuth-vanadate glassy semiconductors. , 1990, Physical review. B, Condensed matter.

[21]  Y. Kobuke,et al.  Highly fluorescent self-coordinated phthalocyanine dimers. , 2005, Angewandte Chemie.

[22]  A. Özkaya,et al.  Synthesis, characterisation and electrochemistry of derivatisable novel α-tetra 7-oxycoumarin-3-carboxylate-substituted metallophthalocyanines , 2011 .

[23]  A. Koca,et al.  Electrochemistry and spectroelectrochemistry of tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine, Lu2Pc4 and dimeric lutetium(III) phthalocyanine, Lu2Pc2(OAc)2 , 2007 .

[24]  N. Mott,et al.  Electronic Processes In Non-Crystalline Materials , 1940 .

[25]  V. Ahsen,et al.  Comparative studies of photophysical and photochemical properties of solketal substituted platinum(II) and zinc(II) phthalocyanine sets , 2010 .

[26]  R. D. Gould,et al.  Investigation of electrical properties (ac and dc) of organic zinc phthalocyanine, ZnPc, semiconductor thin films , 2003 .

[27]  A. Özkaya,et al.  Synthesis, characterization and spectroscopic properties of new fluorescent 7,8-dihexyloxy-3-(4-oxyphenyl)coumarin substituted phthalocyanines , 2009 .

[28]  J. Simon,et al.  Electrochemical reduction of new, good electron acceptors: the metallooctacyanophthalocyanines , 1985 .

[29]  A. R. Ozkaya,et al.  Electrocatalytic activity, methanol tolerance and stability of perfluoroalkyl-substituted mononuclear, and ball-type dinuclear cobalt phthalocyanines for oxygen reduction in acidic medium. , 2009, Dalton transactions.

[30]  Liu,et al.  Limiting behavior of ac conductivity in ionically conducting crystals and glasses: A new universality. , 1991, Physical review letters.

[31]  I. Honma,et al.  A disposable ozone sensor based on a grating-coupled glass waveguide coated with a tapered film of copper tetra-t-butylphthalocyanine , 2005 .

[32]  A. Özkaya,et al.  Preparation, characterization, electrochemistry and in situ spectroelectrochemistry of novel α-tetra[7-oxo-3-(2-chloro-4-fluorophenyl)coumarin]-substituted metal-free, cobalt and zinc phthalocyanines , 2010 .

[33]  A. R. Long.  Frequency-dependent loss in amorphous semiconductors , 1982 .

[34]  J. Sessler,et al.  Guanosine and fullerene derived de-aggregation of a new phthalocyanine-linked cytidine derivative , 2006 .

[35]  Tebello Nyokong,et al.  Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines , 2007 .

[36]  Jian-rong Gao,et al.  One-pot synthesis of coumarin derivatives , 2008 .

[37]  T. Nyokong,et al.  Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines , 2007 .

[38]  Klaus Suhling,et al.  Effects of axial ligands on the photophysical properties of silicon octaphenoxyphthalocyanine , 2002 .

[39]  S. R. Elliott,et al.  A.c. conduction in amorphous chalcogenide and pnictide semiconductors , 1987 .

[40]  V. Ahsen,et al.  Synthesis and solvent effects on the spectroscopic properties of octatosylamido phthalocyanines , 2005 .

[41]  T. Nyokong,et al.  Phthalocyanine. pi. -cation-radical species: photochemical and electrochemical preparation of (ZnPc(-1))/sup. +/ in solution , 1987 .

[42]  Zhen-ya Li,et al.  Temperature dependence of ac response in diluted half-metallic CrO2 powder compact , 2004 .

[43]  K. Lokesh,et al.  Synthesis, characterization, pyrolysis kinetics and conductivity studies of chloro substituted cobalt phthalocyanines , 2007 .

[44]  A. Lever,et al.  Phthalocyanines : properties and applications , 1989 .

[45]  M. Stillman,et al.  Photochemical Formation of the Anion Radical of Zinc Phthalocyanine and Analysis of the Absorption and Magnetic Circular Dichroism Spectral Data. Assignment of the Optical Spectrum of [ZnPc(-3)]- , 1994 .

[46]  A. Lever,et al.  Synthesis, electrochemical and spectroelectrochemical studies of metal-free 2,9,16,23-tetraferrocenylphthalocyanine , 1994 .

[47]  J. Durrant,et al.  Catalysis of recombination and its limitation on open circuit voltage for dye sensitized photovoltaic cells using phthalocyanine dyes. , 2008, Journal of the American Chemical Society.

[48]  M. Durmuş,et al.  Synthesis, photophysical, photochemical and electrochemical properties of crown ether bearing coumarin substituted phthalocyanines , 2012 .

[49]  A. Özkaya,et al.  Synthesis, spectroscopy, electrochemistry and in situ spectroelectrochemistry of partly halogenated coumarin phthalonitrile and corresponding metal-free, cobalt and zinc phthalocyanines , 2009 .

[50]  James S. Shirk,et al.  The Alpha Substitution Effect on Phthalocyanine Aggregation , 1998 .