Esin Hamuryudan

Electrochemical properties of octakis(hydroxyethylthio)-substituted phthalocyanines

Cyclic voltammetry of octakis(hydroxyethylthio)-substituted phthalocyanines with 2H (H2OHETPc), Zn(II) (ZnIIOHETPc(−2)) and Co(II) (CoII(OHETPc(−2)) in the phthalocyanine core has been investigated in dimethylsulfoxide (DMSO), and some of the results were evaluated together with their absorption spectra in the visible range. The redox processes due to both aggregated and non-aggregated species were observed on the voltammograms of phthalocyanines with Zn(II). The effect of chloride ion on the cyclic voltammetry of CoIIOHETPc(−2) has been investigated in the DMSO/ClO4− couple. The comparison of cyclic voltammetry for CoIIOHETPc in the absence and presence of chloride ion showed that chloride ion does not bind to either Co(II) or Co(I) but does bind very strongly to Co(III). The detailed electrochemistry of CoIIOHETPc(−2) was investigated in terms of the Co(I)/Co(II) and Co(II)/Co(III) redox couples, and various equilibria related to the species coordinated to Co(II) and Co(III) in the phthalocyanine core.

Synthesis and Characterization of Octakis (hydroxyethylthio)-substituted Phthalocyanines

The new metal-free phthalocyanine 2 and phthalocyaninatometals 3–5 (M = Ni, Co and Zn) carrying eight hydroxyethylmercapto groups on peripheral positions have been synthesized from 1,2-bis(hydroxyethylmercapto)-4,5-dicyanobenzene in the presence of a suitable anhydrous metal salt [NiCl2, CoCl2 or Zn(O2CMe)2] or hydroquinone. Zinc (II) phthalocyaninate reacted with palladium(II) salt to form complexes with a phthalocyanine (metal ratio of 1:4). The electrical conductivity of the phthalocyanines 2, 3, 5, 5a are in the semiconductor range.

Synthesis of phthalocyanines with tridentate branched bulky and alkylthio groups

Abstract The synthesis and characterisation of 4,5-octasubstituted metal free and metallo (ZnII and CoII) phthalocyanines carrying four alkylthio groups and four tridentate NNS substituents on periferal positions are reported. The distinct differences encountered in the newly synthesized compounds with four alkyl chains are their high solubility in common organic solvents, e.g. chloroform, dichlorometane, THF, acetone, DMF and DMSO and bathochromic shifts in the UV-Vis spectra in comparison with 4,5-substituted analogues with four chloro groups in addition to four branched bulky groups. 1H NMR spectroscopy also shows a smaller up field shift in all protons for newly synthesised phthalocyanines with respect to the latter compounds.

Dioxadiaza macrocycle-substituted phthalocyanines

Abstract New metallophthalocyanines (M=Cu, Ni, Co) have been synthesized from a 16-membered dioxadiaza macrocycle using an anhydrous metal salt (CuCN, NiCl 2 or CoCl 2 ). The new compounds have been characterized by elemental analyses, IR, NMR and electronic spectroscopy.

Synthesis, in situ spectroelectrochemistry and in situ electrocolorimetry of electrochromic octakis(chloroethylsulfanyl) phthalocyaninatomanganese(III) chloride

In this study, the syntheses of octakis(hydroxyethylsulfanyl) phthalocyaninatomanganese(III) chloride and its chlorinated derivative, octakis(chloroethylsulfanyl) phthalocyaninatomanganese(III) chloride, and successive electrochemical investigations of the latter were reported. The voltammetric studies of the complex revealed that it exhibits three one-electron reduction processes and a one-electron oxidation process. In situ spectroelectrochemical studies were performed to decide the origin of the redox processes which are assigned to MnIIIPc2−/MnIIPc2−, MnIIPc2−/MnIPc2−, MnIPc2−/MnIPc3− and MnIIIPc2−/MnIIIPc1− couples, respectively. The presence of oxygen significantly affected the in situ spectroelectrochemical behavior of the complexes due to the formation of μ-oxo MnPc species. An in situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l’Eclairage) system of colorimetry, was applied to investigate the color of the electrogenerated anionic and cationic forms of the complex, which shows solvatochromic properties of the complex in solution. The possible polyelectrochromic application on solid state was suggested due to the color changes from brown to greenish blue and from brown to light yellow of a MnPc-coated thin film on ITO.

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

Summary. Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH3COO)2, NiCl2, and CoCl2. The extremely soluble compounds were characterized by their IR, 1H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines.

Synthesis and in vitro study of new highly boronated phthalocyanine

A new highly boronated Zn(II)-phthalocyanine with eight cobalt bis(dicarbollide) units (144 boron atoms) was prepared and its intracellular accumulation and distribution in GL6 human glioblastoma cells were studied. It was found that the boronated phthalocyanine undergoes strong aggregation in intracellular environment.

o-Carborane, Ferrocene, and Phthalocyanine Triad for High-Mobility Organic Field-Effect Transistors

An unsymmetrical zinc phthalocyanine with ferrocenylcarborane linked to the phthalocyanine ring through a phenylethynyl spacer was designed for organic field-effect transistor (OFET). The unsymmetrical phthalocyanine derivatives were characterized using a wide range of spectroscopic and electrochemical methods. In particular, the ferrocenylcarborane structure was unambiguously revealed based on the single-crystal X-ray diffraction analysis. In-depth investigations of the electrochemical properties demonstrated that the ferrocenylcarborane insertion extended the electrochemical character of ferrocenylcarborane-substituted phthalocyanine (7). Moreover, in the anodic potential scans, the oxidative electropolymerization of etynylphthalocyanine (6) and 7 was recorded. To clarify the effect of the insertion of ferrocenylcarborane (2) on the field-effect mobility, solution-processed films of 2, 6, and 7 were used as an active layer to fabricate the bottom-gate top-contact OFET devices. An analysis of the output and transfer characteristics of the fabricated devices indicated that the phthalocyanine derivative functionalized with ferrocenylcarborane moiety has great potential in the production of high-mobility OFET.

Synthesis and Characterization of Phthalocyanines Containing Four 11-Membered Triaza Macrocycles

New metallophthalocyanines (M=Cu, Zn, Ni or Co) substituted in peripheral positions with four 11-membered triaza macrocycles are prepared from 1,4,7-tris(p-tolylsulfonyl)-1,4,7-triazaheptane and 1,2-dibromo-4,5-bis(bromomethyl)benzene or the corresponding anhydrous metal salt [CuCN, Zn(O2CMe)2, NiCl2 or CoCl2].

Synthesis and photophysical properties of phthalocyanines having calixpyrrole units

Zn2+ and Co2+ metallated phthalocyanines having four calixpyrrole units have been prepared from a calixpyrrole phthalonitrile using Zn2+ or Co2+ salts as templates of a phthalocyanine macrocycle. Host–guest complexes between the anions (Cl−, F− and H2PO4−) and the calixpyrrole units are formed as evidenced by NMR, the shift in the reduction potential of the calixpyrrole units by cyclic voltammetry and by observation of two straight lines in the plot of the conductivity versus the amount of halide. While halides do not form complexes with Zn2+ or Co2+ ions of the phthalocyanine core in the ground state as evidenced by the lack of variation in the position of the Q-band in optical spectroscopy, upon 355 nm excitation, the apical metal–halide complex should be formed as a transient as evidenced by the comparison of the transient absorption spectra in the presence and absence of halides.