Makbule Burkut Koçak

Novel crown ether-substituted phthalocyanines

Abstract A novel macrocycle has been synthesized from 4′-(α-bromoacetyl)benzo-15-crown-5, 4-nitrophthalonitril and diethyl malonate; its cyclotetramerization gives Cu(II), Co(II) and Pd(II) phthalocyanines (Pcs) with four benzo-15-crown-5 substituents on the periphery. The effects of alkali metal cations with these Pcs has been investigated through the changes in the visible spectra. The newly synthesized compounds have also been characterized by elemental analyses, IR, 1 H NMR.

A novel route to 4-chloro-5-alkyl-phthalonitrile and phthalocyanines derived from it

A new route to the synthesis of 4-chloro-5-alkyl-phthalonitrile derivatives was shown by the displacement reaction of 4,5-dichloro-phthalonitrile and diethylmalonate, a CH-acidic precursor, in the presence of K2CO3. Cyclotetramerization of 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxy-methyl)benzene and the metal salt without any solvent gave the corresponding metallophthalocyanines (M = Co, CuorPd). Transesterification occurred when the reaction was carried out in hexanol in the presence of DBU to obtain the metal-free derivative. Treatment of 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxy-methyl)benzene with sodium ethoxide at ambient temperature and further acidification resulted in 2,9,16,23-tetra(carboxymethyl)-3,10,17,24-tetrachloro-phthalocyaninatopalladium(II) with partial decarboxylation. Its electronic spectrum in aqueous solution indicated no appreciable change over a pH range from 7 to 12.

Novel two-fold-macrocycle-substituted phthalocyanines

New metallophthalocyanines (M = Cu or Ni) substituted in peripheral positions with four 14-membered tetraaza macrocycles each attached to a 15-membered crown ether have been prepared in a multi-step reaction sequence. The N-tosylated derivatives are extensively soluble in apolar solvents and form adducts with alkali-metal cations. Detosylation of the macrocyclic aza groups provides donor sites for binding transition-metal ions (e.g. NiII) which leads to pentanuclear water-soluble complexes.

Synthesis of tetra(tricarbethoxy)- and tetra(dicarboxy)- substituted soluble phthalocyanines

Pd(II), Co(II), Cu(II) and Zn(II) phthalocyanines with a tricarbethoxyethyl substituent on each benzo group were prepared from 4-(1,1,2-tricarbethoxyethyl)-phthalonitrile and the corresponding divalent metal salt at 170 °C. Transesterification occurred when the reaction was carried out in pentanol. Treatment of the palladium complex with sodium ethoxide at room temperature and further acidification resulted with tetra(1,2-dicarboxyethyl)phthalocyaninatopal- ladium. Its UV-vis spectrum in aqueous solution indicated dimeric and monomeric species at pH ≈ 12, but at pH ≈ 6 only the dimeric form were present. Copyright

Synthesis of New Metal-Free and Metal-Containing Phthalocyanines with Tertiaryor Quaternary Aminoethyl Substituents

Summary. A novel phthalodinitrile derivative carrying dimethylaminoethylsulfanyl groups at positions 4 and 5 was synthesized from 2-dimethylaminoethanethiol hydrochloride and 1,2-dichloro-4,5-dicyanobenzene. Its cyclotetramerization in the presence of 2-dimethylamino-ethanol or metal salts (CoCl2, Zn(OAc)2) gave metal-free or metal-containing phthalocyanines (M = Co or Zn). These phthalocyanines were converted into water soluble quaternized products by reaction with methyl iodide. The new compounds were characterized by elemental analysis, IR, NMR, and electronic spectra.

Electrochemical characterization of Co(II) and Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents

In this study, electrochemical behaviors of Co(II) and Pd(II) phthalocyanines carrying tetrakisdiethoxymalonyl and Pd(II) phthalocyanine carrying tetrakiscarboxymethyl substituents at the peripheral positions are investigated by cyclic voltammetry and applied potential chronocoulometry techniques. Cyclic voltammetric studies show that, while Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents give up to three common phthalocyanine ring reductions, Co(II) phthalocyanine carrying diethoxymalonyl substituents gives a metal-centered oxidation and a metal-centered reduction and three ligand-centered reduction and a ligand-centered oxidation processes. First reduction processes of both the PdPc complexes have shoulders. This different voltammetric behaviors of Pd(II) phthalocyanines carrying carboxymethyl and diethoxymalonyl substituents results from interaction of this distinctive substituents with the phthalocyanine ring π electron system and interaction with the different solvent systems. Observation of the splitting of the first reduction process of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents suggests the aggregation of the complex. Very small diffusion coefficient of the complexes with respect to Co(II) phthalocyanine also confirms the existence of the aggregation of the complex during the electrochemical studies. Effects of the substituents and the solvent media are clearly observed from the differences of the voltammograms of Pd(II) phthalocyanines carrying diethoxymalonyl and carboxymethyl substituents in DMSO and THF solvent media, respectively.

Synthesis and characterization of novel phthalocyanines substituted with four tetraaza macrocycles

A novel copper phthalocyanine substituted with four 14-membered tetraaza macrocycles and its pentanuclear nickel(II) complex were synthesized and characterized by elemental analysis, and IR and UV spectroscopy.

Synthesis and spectral properties of tetra- and octa-substituted lead phthalocyanines

The novel four lead phthalocyanines were prepared from three different phthalonitrile derivatives, namely 3,4-dicyanophenylmalonate, 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxy-methyl)benzene, 1-hexylthio-3,4-dicyano-6-(1,1-dicarbethoxy-methyl) benzene and metal salts (PbO or Pb(OAc)2·3H2O). Transesterification occurred when the reaction was carried out in hexanol in the presence of DBU. These new lead-phthalocyanines have been characterized by 1H NMR, FT-IR, UV-Vis and mass spectra. Two common points in these lead phthalocyanines are intense Q band absorptions in the near-IR region and relatively lower stability of the metal ion in the phthalocyanine cavity.

Anionic water-soluble sulfonated phthalocyanines: microwave-assisted synthesis, aggregation behaviours, electrochemical and in-situ spectroelectrochemical characterisation

Abstract In this work, a phthalonitrile derivative bearing p-sulfonylphenoxy group at the 3-position has been synthesised. The water-soluble non-peripherally tetrasubstituted zinc (3) and cobalt (4) phthalocyanines were obtained by cyclotetramerisation of this phthalonitrile derivative in the presence of anhydrous metal salts by microwave irradiation. The compounds have been characterised by using FT-IR, 1H NMR, UV–Vis and Mass spectrometry (MS) data. The aggregation behaviours of these compounds were investigated in methanol, DMSO, DMF, and water. We have also studied the aggregation behaviours of the phthalocyanine complex 3 in various DMSO/water mixtures. Additionally, the redox properties of the phthalocyanine complexes were examined in dimethylsulfoxide by voltammetry and in situ spectroelectrochemistry. Redox behaviours of the complexes supported the structures of the complexes. Metal and ring-based reductions were observed for 4 and only ring-based electron transfer processes were observed with 3.

Synthesis and Complexation of a Novel Soluble vic -Dioxime Ligand

Summary. A new soluble vic-dioxime 1,4-(isobutyl)-2,3-bis-(hydroxyimino)-5,6-phenylpiperazine was prepared as a mixture of isomers from anti-dichloroglyoxime and N,N′-bis-(isobutyl)-stilbendiamine which reacts to N,N′-coordinated planar metal complexes with Ni(II), Cu(II), Co(II), and Pd(II). Oxidation of the Co(II) complex in the presence of pyridine leads to an octahedral complex containing pyridine and chloride as axial ligands in addition to the vic-dioxime ligands. The uranyl complex has a 1:1 metal:ligand ratio and a dinuclear structure with μ-hydroxo bridges.