Ergün Gonca

Partially oxidized porphyrazines

Magnesium porphyrazinate substituted with eight (1-naphthyl) groups on the peripheral positions has been synthesized by cyclotetramerization of 3,4-(1-naphthyl)pyrroline-2,5-diimine, 4-(1-naphthyl)pyrroline-2,5-diimine in the presence of magnesium butanolate. Its demetalation by treatment with trifluoroacetic acid, resulted in a partially oxidized product, namely, octakis(1-naphthyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate led to the metallo derivatives, [octakis(1-naphthyl)-2-seco-2,3-dioxoporphyrazinato]M(II) (M = Cu, Zn or Co). These new compounds have been characterized by elemental analysis, together with FT-IR, 1H NMR, UV-vis and mass spectral data.

Synthesis and characterization of soluble seco-porphyrazines with bulky substituents

By cyclotetramerization of 3,4-bis(4-tert-butylphenyl)pyrroline-2,5-diimine in the presence of magnesium butanolate, magnesium porphyrazinate with eight (4-tert-butylphenyl) units on the periphery has been synthesized. Its demetalation by the treatment with trifluoroacetic acid resulted in a partially oxidized product, namely, octakis(4-tert-butylphenyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate, and cobalt(II) acetate led to the metallo derivatives, [octakis(4-tert-butylphenyl)-2-seco-2, 3-dioxoporphyrazinato]M(II) (M = Cu, Zn, Co). These soluble complexes have been characterized by elemental analysis, FT-IR, 1H NMR, UV-Vis, and mass spectral data.

Seco-porphyrazines with eight (p-tolyl) and (o-tolyl) units

Magnesium porphyrazinates substituted with eight (p-tolyl) and (o-tolyl) units on the peripheral positions have been synthesized for the first time by cyclotetramerization of 1,2-bis(p-tolyl)maleonitrile and 1,2-bis(o-tolyl)maleonitrile in the presence of magnesium butanolate. Their demetalation by the treatment with trifluoroacetic acid resulted in partially oxidized products, namely, octakis(p-tolyl)-2-seco-porphyrazine-2,3-dione and octakis(o-tolyl)-2-seco-porphyrazine-2,3-dione. Further reactions of these products with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate have led to the metallo derivatives, [octakis(p-tolyl)-2-seco-2,3-dioxoporphyrazinato]M(II) and [octakis(o-tolyl)-2-seco-2,3-dioxoporphyrazinato]M(II) (M = Cu, Zn, Co). These novel compounds have been characterized by elemental analysis, together with FT-IR, 1H NMR, UV-vis and mass spectral data.

New soluble porphyrazine derivatives containing electron-rich substituents

Hydroxypropylsulfanyl groups of metal-free and metallo-porphyrazines (M=2H, Mg, Cu, Zn, or Co) have been prepared by the esterification with a carboxylate such as 1-naphthoic acid. The symmetrically functionalized porphyrazines with eight ester units were soluble in common organic solvents such as CHCl3, CH2Cl2, tetrahydrofuran, acetone, and toluene and insoluble in water and n-hexane. The compounds have been characterized by FT-IR, UV–Vis, mass, 1H, 13C NMR, and elemental analysis.

Voltammetric and spectroelectrochemical characterization and electrocatalytic application of metallophthalocyanines carrying pendant bulky units

In this work, voltammetric, spectroelectrochemical, and electrocatalytic properties of the metallophthalocyanines bearing four chloro and four biphenyl-malonic ester bulky groups were investigated. Voltammetric and spectroelectrochemical measurements of the metallophthalocyanines show that while cobalt phthalocyanine presents both metal-based and ring-based redox processes, all other complexes give only ring-based reduction and oxidation processes. The redox processes have generally diffusion-controlled, reversible and one-electron transferred mechanisms. Cobalt phthalocyanine electrocoated easily on the glassy carbon working electrode during the repeating cycles, a very useful feature for application in fabrication of thin films. Electrocatalytic activity of cobalt phthalocyanine to hydrogen evolution reaction was studied in solution titrated with perchloric acid and on glassy carbon electrode modified with cobalt phthalocyanine in aqueous solution. Electrocatalytic measurements show that cobalt phthaloc...

Synthesis and characterization of soluble porphyrazines bearing octakis 2-anthraquinonylmethylthio substituents

By cyclotetramerization of 1,2-bis(2-anthraquinonylmethylthio)maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2-anthraquinonylmethylthio) functional groups on peripheral positions has been synthesized. The metal-free derivative was obtained by treatment with trifluoroacetic acid; reaction of this product with copper(II) acetate, zinc(II) acetate, and cobalt(II) acetate led to the metal porphyrazinates [M = Cu(II), Zn(II), and Co(II)]. These new compounds have been characterized by elemental analysis, together with FT-IR, 1H-NMR, 13C-NMR, UV-Vis, and mass spectral data.

Monomeric and Homoleptic Thorium Porphyrazine Derivatives

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