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The content of this work is based on the introduction of the salicylhydrazone-zinc complexes into the phthalocyanine core. The reaction of the salicylhydrazone substituted ZnPc (1) with the related zinc(II) salt in basic conditions in DMF yielded bis[bis(salicyhydrazone)phenoxy)zinc(II)] phthalocyaninato zinc(II) (5) in which two salicylhydrazone-Zn complexes are linked through oxygen bridges to the macrocyclic core as three-nuclear complex. The novel compound synthesized in this study was fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, 1H NMR, 13C NMR, elemental analysis and mass spectroscopy. In addition, spectral, photophysical (fluorescence quantum yields), and photochemical (generation of singlet oxygen and photo stability under light irradiation) properties of newly synthesized phthalocyanine (5) and the starting Pcs molecules used to obtain this molecule were investigated in DMSO solutions, comparatively.

The context of this study is based on the synthesis of tetrakis{4-(2-([2,2[Formula: see text]:6[Formula: see text],2[Formula: see text]-terpyridine]Zn(II)-4[Formula: see text]-yl(methyl)amino)ethoxy)}phthalocyaninato zinc (II) (3) bearing four terpyridine-Zn(II) complexes that are directly linked through oxygen bridges to the macrocyclic core in order to create new supramolecular assemblies. The target phthalocyanine (3) was obtained by cyclotetramerization reaction of terpyridine-Zn (II) complex substituted phthalonitrile (2). All novel compounds synthesized in this study were fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, and [Formula: see text]H-NMR, [Formula: see text]C-NMR, elemental analysis and mass spectroscopy. Spectral, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen production and photodegradation under light irradiation) properties of newly synthesized phthalonitrile (2) and its phthalocyanine derivative (3) as five nuclear phthalocyanine were investigated in DMSO solutions.

This study covers the functional complexes of tetrakis [4-(salicyhydrazone)phenoxy)] phthalocyaninato cobalt (II) (5) which was the macro molecular Schiff base ligand and synthesized through a multistep reaction sequence starting first with the cyclotetramerization of 4-[4-(1,3-Dioxolan-2-yl)phenoxy]-phthalonitrile (2). Then, the de-protection of tetra acetal groups of Tetrakis[4-(1,3-dioxolan-2-yl)phenoxy)]phthalocyaninato cobalt (II) (3) to the aldehyde functionality in acetic acid/FeCl3 system to yield the Tetrakis(4-formylphenoxy)phthalocyaninato cobalt(II) (4) and then its condensation with salicylhydrazide gave to 5. Finally, CoPc-bis(salicyhydrazone)phenoxy)manganese (III) (6), CoPc-bis(salicyhydrazone) phenoxy)cobalt(III) (7) and CoPc-bis (salicyhydrazone)phenoxy) nickel(II) (8) were synthesized using with the related MnCl2·4H2O, CoCl2·6H2O, Ni(CH3COO)2 salt in basic conditions in DMF. FT-IR, UV–Vis, MS spectra and elemental analysis were applied to characterize to prepared compounds. The bleaching performances of the prepared phthalocyanine compounds (3–8) were examined by the degradation of Morin as the hydrophilic dye which characterized the wine stains on the fabrics. Progress of the degradations in the catalysts (3–8)/H2O2 combination in basic aqueous solution conditions was investigated by using online spectrophotometric method (OSM). It was found that the prepared catalysts showed better bleaching performance at 25 °C than to that of tetraacetylethylenediamine (TAED) bleach activator commercially used in powder detergent formulations.

This study reported the oxidative degradation of morin dye with hydrogen peroxide catalyzed by manganese phthalocyanines as low temperature bleaching catalysts for laundry applications. A novel series of manganese phthalocyanines (MnPcs) have been synthesized starting with tetrakis[4-(1,3-dioxolan-2-yl)phenoxy)]phthalocyaninatomanganese(III) (2) prepared by the cyclotetramerization of 4-[4-(1,3-dioxolan-2-yl)phenoxy]-phthalonitrile (1). De-protection of acetal groups of 2 to the aldehyde group in an acetic acid/FeCl3 system yielded the tetrakis(4-formylphenoxy)phthalocyaninatomanganese(III) (3). The condensation of 3 with 3-(dimethylamino)-1-propylamine gave Schiff base-substituted Mn(III)Pc 4. Finally, quaternization of the dimethylamino functional groups with the reaction of methyl iodide produced cationic manganese(III) phthalocyanine 5 which was soluble in both DMSO and water. These new MnPcs were characterized by the combination of spectroscopic methods (FT-IR, UV-Vis and mass spectroscopy). The effects of structural variables of the prepared compounds (2-5) on their dissolution in the solvent system LiCl/DMAc-DMF-DMSO and THF were also investigated. Degradation of morin at 25and 40 degrees C in the presence of catalysts (2-5)/H2O2 combination in basic medium was examined by online spectrophotometric method, and the bleaching activities of the prepared compounds have been evaluated comparatively. It was found that the prepared catalysts have more effective bleaching performance at 25 degrees C than tetraacetylethylenediamine (TAED) which is a bleach activator commercially used in powder detergent formulations.

Erratum to Acta Cryst. (2018), E74, 1517–1520., In the paper by Sen et al. [Acta Cryst. (2018), E74, 1517–1520], the address of the correspondence author is incorrect.

In the crystal, the crystal packing is ordered via synergetic contributions from N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonds, which together assemble the cations and anions into a three-dimensional framework., The asymmetric unit of the title compound, C8H11N3 2+·2Cl−·H2O, contains three organic cations, six chloride anions and three water mol­ecules of crystallization, which are connected by extensive hydrogen-bonding inter­actions into a three-dimensional supra­molecular architecture. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (37.4%), Cl⋯H/H⋯Cl (35.5%), C⋯H/H⋯C (9.5%) and C⋯C (6.9%) inter­actions.

kanmazalp, sibel demir/0000-0002-5896-0966; Dege, Necmi/0000-0003-0660-4721; WOS: 000415292500019 The context of this study is based on the synthesis of 4-(4-(1H-benzo[d] imidazole-2yl) phenoxy group substituted phthalocyanine (4) and 4-(4-(1-allyl-1H-benzo[d] imidazole-2yl) phenoxy group substituted phthalocyanine (5). These phthalocyanine derivatives (4, 5) are reported for the first time with four functional groups containing benzimidazole derivatives that are linked through oxygen bridges to the macrocyclic core. All novel compounds synthesized in this study were fully characterized by general spectroscopic techniques such as FT-IR, UV-vis, H-1 NMR, C-13 NMR, elemental analysis and mass spectroscopy. The compound 4-(4-(1-allyl-1H-benzo[d] imidazole-2yl) phenoxy) phthalonitrile (3) was obtained as single crystal and exact structure of these compounds have also been determined using X-ray diffraction technique at 296 K. Weak intra and intermolecular C-H center dot center dot center dot N interactions and a C-H center dot center dot center dot pi interaction link molecules into a three-dimensional network. Then, spectral, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of the new complexes were investigated in DMSO solutions. These new phthalocyanines (4 and 5) showed good singlet-oxygen generation (Phi(Delta) = 0.65 for 4 and Phi(Delta) = 0.68 for 5) in DMSO. Sakarya UniversitySakarya University [2014-02-04 007] This work was supported by Research Fund of Sakarya University (project no. 2014-02-04 007).

kanmazalp, sibel demir/0000-0002-5896-0966; Dege, Necmi/0000-0003-0660-4721 WOS: 000454871700010 The context of this study is based on the synthesis of 4-(4-(1H-benz[d]imidazol-2-yl)phenoxy group substituted phthalonitrile (2), 4-(4-(1-allyl-1H-benz[d]imidazol-2-yl)phenoxy group substituted phthalonitrile (3) that were reported for the first time. These phthalonitrile derivatives were also converted to the corresponding cobalt(II) and manganese(III) phthalocyanines (4-7) with four nitrogen-containing groups which helped to stabilize the redox active metal during the oxidation process. All novel compounds synthesized in this study were fully characterized by general spectroscopic techniques such as FT-IR, UV-Vis, H-1 NAIR, C-13 NAIR spectroscopy and mass spectrometry. The compounds 2-(4-hydroxyphenyObenzimidazole (1) and 4-(4-(1-allyl-1H-benz[d]imidazol-2-yl)phenoxy group substituted phthalonitrile (3) were obtained as single crystal and exact structure of these compounds has also been determined using X-ray diffraction technique at 296 K. Bleach catalyst activity of the prepared phthalocyanine complexes (4-7) was examined by degradation of morin. The catalysts had better activity for color removing in solutions at ambient temperature than to that of tetraacetylethylenediamine (TAED). Ministry of Science, Industry and Technology of TurkeyMinistry of Science, Industry & Technology - Turkey [0182.STZ.2013-1]; Research Fund of Sakarya UniversitySakarya University [2014-02-04 007] This work was supported by Ministry of Science, Industry and Technology of Turkey (SANTEZ project no. 0182.STZ.2013-1) and Research Fund of Sakarya University (project no. 2014-02-04 007).

Dege, Necmi/0000-0003-0660-4721; WOS: 000362959200008 PubMed: 26215079 A new highly fluorescent difluoroboradipyrromethene (BODIPY) dye (4) bearing an phthalonitrile group at meso-position of the chromophoric core has been synthesized starting from 4-(4-meso-dipyrromethene-phenoxy)phthalonitrile (3) which was prepared by the oxidation of 4-(2-meso-dipyrromethane-phenoxy)phthalonitrile (2). The structural, electronic and photophysical properties of the prepared dye molecule were investigated. The final product exhibit noticeable spectroscopic properties which were examined by its absorption and fluorescence spectra. The original compounds prepared in the reaction pathway were characterized by the combination of FT-IR, H-1 and C-13 NMR, UV-vis and MS spectral data. It has been calculated; molecular structure, vibrational frequencies, H-1 and C-13 NMR chemical shifts and HOMO and LUMO energies of the title compound by using B3LYP method with 6-311++G(dp) basis set, as well. The final product (4) was obtained as single crystal which crystallized in the triclinic space group P-1 with a = 9.0490 (8) , b = 10.5555 (9) , c = 11.7650 (9) , alpha = 77.024 (6)angstrom, beta = 74.437 (6)angstrom, gamma = 65.211 (6)angstrom and Z = 2. The crystal structure has intermolecular C-H center dot center dot center dot F weak hydrogen bonds. The singlet oxygen generation ability of the dye (4) was also investigated in different solvents to determine of using in photodynamic therapy (PDT). Ministry of Science, Industry and Technology of Turkey (SANTEZ)Ministry of Science, Industry & Technology - Turkey [0182.STZ.2013-1]; Sakarya UniversitySakarya University [2014-02-04 007] This work was supported by Ministry of Science, Industry and Technology of Turkey (SANTEZ project no. 0182.STZ.2013-1) and Research Fund of Sakarya University (project no. 2014-02-04 007).

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost-effective, energy-saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) (), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) () and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) () as tri-nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes was performed through the reaction of a Schiff base-substituted phthalocyanine using MnCl2⋅4H2O, CoCl2⋅6H2O or FeCl3⋅6H2O salts in basic condition in dimethylformamide. Fourier transform infrared, 1H NMR, 13C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts /H2O2 combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.

Dege, Necmi/0000-0003-0660-4721; ATAKAY, MEHMET/0000-0002-7102-2974 WOS: 000398581000005 The present study dealing with the oxidation catalysts using in laundry bleaching process comprises of the complexion of 4'-(N-2-phthalonitrile-N-methylamino)-2,2':6',2''-terpyridine (2) with the related MnCl2.4H(2)O and CoCl2.6H(2)O salts in ethanol to obtain 4'-(N-2-phthalonitrile-N-methylamino)-2,2':6',2''-terpyridine-Mn (II) complex (3) and 4'-(N-2-phthalonitrile-N-methylamino)-2,2':6',2''-terpyridine-Co (II) complex (4). Terpyridine metal complexes substituted Zinc phthalocyanines, Tetrakis [4'-(N-2-phthalonitrile-N-methylamino)-2, 2': 6', 2''-terpyridine-Mn(II) complex] phthalocyaninato zinc(II) (5) and Tetrakis [4'-(N-2-phthalonitrile-N-methylamino)-2,2':6',2''-terpyridine-Co(II) complex] phthalocyaninato zinc(II) (6) were also prepared by the tetramerization of the terpyridine-metal complexes (3, 4) in the presence of ZnCl2. FT-IR, H-1-NMR, C-13-NMR, UV-Vis, ESI-MS and MALDI-MS spectra were applied to characterize the prepared compounds. 4-nitrophthalonitrile and some other starting materials crystallized in the synthetic pathway. 4-nitrophthalonitrile crystalizes in different morphology and 4'-(N-2- Hydroxyehyl-N-methylamino)-2, 2' : 6', 2''- terpyridine (1) crystallizes in the monoclinic, space group. The compound 2 and 3 crystallize in the monoclinic space group. The bleach performances of the prepared terpyridine complexes (3, 4) and their phthalocyanine derivatives (5, 6) were examined by the degradation of Morin dye by using online spectrophotometric method (OSM). Ministry of Science, Industry and Technology of TurkeyMinistry of Science, Industry & Technology - Turkey [0182.STZ.2013-1]; Research Fund of Sakarya UniversitySakarya University [2014-02- 04 007] This work was supported by Ministry of Science, Industry and Technology of Turkey (SANTEZ project no. 0182.STZ.2013-1) and Research Fund of Sakarya University (project no. 2014-02-04 007).

A phthalocyanine (4) with four salicylhydrazone ligating groups that are directly linked through oxygen bridges to the macrocyclic core has been synthesized by condensation of tetrakis(4-formylphenoxy)phthalocyaninato zinc(II) (3) with salicylhydrazine. Salicylhydrazine was crystallized in methanol during the synthetic procedure. The crystal structure has triclinic space group P-1 with a = 5.8292(6) Å, b = 7.3039(7) Å, c = 17.9798(18) Å, α = 84.272(8)°, β = 89.184(8)°, γ = 81.469(8)°, and Z = 4. Intramolecular O–H⋯O and intermolecular O–H⋯O, N–H⋯N, N–H⋯O hydrogen bonds were determined in the crystal structure. In addition, there is a weak C–H⋯π interaction. Complexation on the periphery to yield tri-nuclear Zn(II)Pcs (5–7) was performed through the reaction of a Schiff base-substituted phthalocyanine (4) with MnCl2·4H2O, CoCl2·6H2O, or Ni(OAc)2 salts. Fourier transform infrared, 1H NMR, 13C NMR, UV–Vis, ICP-OES (inductively coupled plasma optical emission spectroscopy), mass spectroscopies, and elemental analyses were applied to characterize the prepared compounds. Bleach catalyst activity of the prepared phthalocyanine complexes (5–7) was examined by the degradation of morin and curcumin, respectively. The catalysts had better activity for color removing in solutions at ambient temperature than to that of tetraacetylethylenediamine (TAED).

The molecular structure, natural bond orbital (NBO) analysis and vibrational studies of Sudan Red G {(SRG), [1-(2-methoxyphenylazo)-2-naphthol]} have been investigated using Density Functional Theory (DFT) calculations. To investigate the tautomeric stability, optimisation calculations at the Hartree–Fock (HF) and DFT/B3LYP levels were performed for the azo (OH) and hydrazo (NH) forms of the title compound. FT-IR, FT-Raman and electronic absorption spectra of SRG have recorded and analysed. We have compared the calculated IR and Raman wavenumbers with the observed data. A novel copper(II) coordination compound with Sudan Red G was synthesised and characterised by analytical, spectroscopic (FT-IR and electronic absorption spectra) and single-crystal X-ray diffraction methods. The X-ray structure of the prepared coordination compound indicated that it crystallised in a dimeric form as [Cu2(SRG)4� 2O0.5] that consists of facial geometric isomer. In the coordination compound, the Cu(II) atoms have a distorted octahedral geometry.

The context of this study is based on the synthesis of tetrakis[salicyoxy-salicyhydrazone] phthalocyaninato zinc(II) ( 4 ), with four salicylhydrazone ligating groups that are directly linked through oxygen bridges to the macrocyclic core, and its tri-nuclear Zn(II) Schiff base complex Bis[bis(salicyoxy-salicyhydrazone)zinc(II)]phthalocyaninato zinc(II) ( 5 ) starting from tetrakis(2-formylphenoxy)phthalocyaninato zinc(II) ( 3 ) which was obtained with an improved yield via de-protection of tetra acetal-substituted phthalocyanine tetrakis[2-(1,3-dioxolan-2-yl)phenoxy]phthalocyaninato]zinc(II) ( 2 ) in acetic acid/FeCl 3 system. The substituted zinc phthalocyanine ( 2 ) was prepared by the tetramerization of 4-[2-(1,3-dioxolan-2-yl) phenoxy] phthalonitrile ( 1 ) in the presence of the related metal salts. Complexion on the periphery to obtain trinuclear complex ( 5 ) has been performed through the reaction of the Schiff base substituted phthalocyanine ( 4 ) with the related zinc (II) salt in basic conditions in DMF. FT-IR, 1 H NMR, 13 C NMR, UV–Vis, ICP-OES and MS spectra were applied to characterize the prepared compounds. The fluorescence properties and quantum yields of the prepared complexes were investigated. The aggregation properties of the target phthalocyanines were also examined.

This comparative study is based on the preparation of Bis[bis(tris(hydroxymethl)iminomethane-phenoxy)manganese(III)]phthalocyaninato zinc(II) (3) and Bis[bis(tris(hydroxymethyl)iminomethane-phenoxy) cobalt(III)] phthalocyaninato zinc(II) (4) as the tri-nuclear complexes consist of two Schiff base complexes substituted Zn-Phthalocyanine for bleach catalysis. Complexion on the periphery to obtain the complex (3-4) has been performed through the reaction of the Schiff base substituted phthalocyanine tetrakis [tris(hydroxymethyl)iminomethane-phenoxy] phthalocyaninato zinc(II) (2) by using MnCl2 center dot 4H(2)O and CoCl2 center dot 6H(2)O salts in basic condition in DMF.FT-IR, H-1 NMR, C-13 NMR, UV-vis, ICP-OES and MS spectra were applied to characterize the prepared compounds. The bleaching performances of the prepared phthalocyanine compounds (3-4) were examined by the degradation of Morin as hydrophilic dye characterizes the wine stains. The degradation progress in the presence of catalysts (3-4)/H2O2 combination in aqueous solution buffered with Na2CO3 to provide the detergent characteristic has been investigated using online spectrophotometric method (OSM). It was found that the prepared catalysts exhibited better bleaching performance at 25 degrees C than to that of tetraacetylethylenediamine (TAED) as bleach activator commercially used in powder detergent formulations. (C) 2016 Elsevier B.V. All rights reserved.

Demirtas, Gunes/0000-0001-9953-4026; Dege, Necmi/0000-0003-0660-4721 WOS: 000333788900048 A novel 4-(2-meso-BOBIPY-phenoxy)phthalonitrile (6) derivative has been synthesized starting from BF3-OEt2 complex and 4-(2-meso-dipyrromethene-phenoxy)phthalonitrile (5) which was prepared by the oxidation of 4-(2-meso-dipyrromethane-phenoxy)phthalonitrile (4). The final product exhibit noticeable spectroscopic properties which were examined by its absorption and fluorescence emission spectra. The original compounds prepared in the reaction pathway were characterized by the combination of FT-IR, H-1 and C-13 NMR, UV-vis, MS and HRMS spectral data. The final product (6) was obtained as single crystal which crystallized in the triclinic space group P-1 with a=7.9411 (6) angstrom, b=9.0150 (6)angstrom, c=14.419 (1) angstrom, alpha=74.917 (5)degrees, beta=86.824 (6)degrees, gamma=84.109 (5)degrees and Z=2. The crystal structure has intermolecular C-H center dot center dot center dot F-B and C-H center dot center dot center dot N interactions. These interactions construct bifurcated hydrogen bonds in the crystal structure. In this study, It has been calculated; molecular structure, vibrational frequencies, H-1 and C-13 NMR chemical shifts and HOMO and LUMO energies of the title compound by using B3LYP method with 6-311 + + G(dp) basis set, and the electronic spectral characterization was investigated for the target product, as well. (C) 2014 Elsevier B.V. All rights reserved. Sakarya UniversitySakarya University [2012-02-04-034]; Ondokuz Mayis UniversityOndokuz Mayis University This study was supported by the Research Fund of Sakarya University, Project no. 2012-02-04-034. The authors also thank Ondokuz Mayis University Research Fund for financial support of the project.

New metal-free 5 and metallophthalocyanines 6-11( M = Cu , Ni , Co , Pb , Zn ) fused in peripheral positions with four 24-membered tetraoxatetraaza macrocycles were prepared by cyclotetramerization of 24,25-dicyano-4,10,13,17-tetra(toluene-p-sulfonyl)-1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22-didicontinehydrobenzo[y][3,9,12,18]tetraaza[1,7,16,22]tetraoxatetradicontine in the presence of the corresponding metal salt or a strong organic base. While the N-tosylated derivatives of the phthalocyanines are soluble in common organic solvents, the detosylated derivative of copper phthalocyaninate is soluble in water. The aggregation properties of the phthalocyanines were also investigated as a function of concentration, solvent and oxidative medium. The new compounds are characterized by a combination of elemental analysis and 1 H NMR, 13 C NMR, IR, UV-vis and MS spectral data.

Lithium metal added to a solution of 4-neopentoxyphthalonitrile in 1-octanol or other long-chain primary alcohols at room temperature resulted in phthalocyanine formation at a reasonable rate in good yield, while preformed lithium 1-octanolate under the same conditions gave 2,9,16,23-tetraneopentoxyphthalocyanine, but in lower yield at a slower rate. The use of lower-molecular-weight alcohols slowly gave a phthalocyanine in lower yields. Reverse micelle formation when using long-chain alcohols is proposed as a possibility for enhanced phthalocyanine formation at room temperature. 2,9,16,23-Tetrasubstituted phthalocyanines and metallated phthalocyanines were prepared at room temperature from 4-neopentoxyphthalonitrile, 4-bis(4-methoxyphenyl)methoxyphthalonitrile, 4-[1-(4-ethoxy-3-methoxyphenyl)-1-phenyl]methoxyphthalonitrile and phthalonitrile using lithium 1-octanolate in 1-octanol or by the addition, to a solution of the phthalonitrile in ethanol, of calcium turnings or, to a solution of the phthalonitrile in methanol, of magnesium, zinc, iron or copper powder. The tetrasubstituted phthalocyanines produced exhibited a non-statistical distribution of regioisomers, indicating that electronic effects become important in room-temperature cyclotetramerization of phthalonitriles to phthalocyanines.

The synthesis and characterization of novel metal-free (8) and metal-containing (Cu, Ni or Co, 6, 9, 10) derivatives of a symmetrically tetrasubstituted phthalocyanine derived from 17,18-dicyano-4,8,12-tri(toluene-p-sulfonyl)-1,2,3,4,5,6,7,8,9,10,11,12,13,14,15-pentadecahydrobenzo[1.15]dioxa[4.8.12]tetraazacycloheptadecine (7), which was synthesized in a multi-step reaction sequence, have been described. The N-tosylated derivatives are highly soluble in common organic solvents. The new compounds have been characterized by elemental analyses, 1H and 13C NMR, IR, UV/VIS and MS spectral data.

Copper(II) phthalocyanine containing four 17-membered dioxa-triaza macrocycles has been synthesized starting from copper(II) phthalocyanine substituted 1,2-bis(ethoxycarbonylmetoxy) and 3,3′-diaminodipropylamine. This copper(II) phthalocyanine was used in the extraction of alkali metals and alkaline earth metal picrates from aqueous media. The structures of the compounds are proposed according to elemental analysis, 1H, 13C NMR, IR, UV-VIS and MS spectral data.

New metal-free 3 and metallophthalocyanines 4–5 (M = Ni or Zn) substituted with four 20-membered tetraaza-dioxa macrocycles from 21,22-dicyano-2,8,11,17-tetra-(toluene-p-sulfony)-1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18-octadecahydrox[l] [2,8,11,17]tetraaza [4,13]dioxadicontine (2) are described. Cyclotetramerization of the substituted phthalonitrile (2) leads to a product very soluble in common organic solvents. The characterization of the compounds was accomplished by elemental analysis, 1H, 13C NMR, IR, UV-vis and MS spectral data.

The synthesis and characterization of a copper(II) phthalocyanate substituted with four 20-membered tetraaza-dioxa macrocycles from 21,22-dibromo-2,8,11,17-tetra(toluene-p-sulphonyl)-1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18-octadecahydrobenzox[l] [2,8,11,17]tetraaza[4,13]dioxacyclodi-contine is described. The detosylation of the macrocyclic aza groups provides four tetraaza-dioxa mixed donor sites for binding metal ions. The structures of the compounds were determined by elemental analysis, 1H, 13C NMR, IR and MS spectral data.

Reduction of 2,3:9,10-dibenzo-5,12-diaza-1,8-dioxacylotetradecane-5,11-diene(1) with sodium borohydride in ethanol generates 2,3:9,10-dibenzo-5,12-diaza-1,8-dioxacyclotetradecane(2) in high yield. The macrocyclic ligand 2,3:9,10-dibenzo-5,12-diaza-1,8-dioxacyclotetradecane-N,N′-diacetic acid (3) has been synthesized and characterized. In addition, reaction of (2) with an excess of acrylonitrile gives 2,3:9,10-dibenzo-5,12-diaza-1,8-dioxacyclotetradecane-N,N′-di(2-cyanoethyl) (4). Several new complexes of these ligands with nickel(II), copper(II) and cobalt(II) have been prepared and identified. The structures of these complexes are proposed on the basis of elemental analysis, 1H, 13C-NMR, IR, UV-VIS spectra, magnetic susceptibility and conductivity data. Synthese und Metallkomplexbildung von makrozyklischen Stickstoff-Sauerstoff-Donorliganden Die Reduktion von 2,3:9,10-Dibenzo-5,12-diaza-1,8-dioxacyclotetradecan-5,11-dien(1) mit Natriumborhydrid in Ethanol ergibt 2,3:9,10-Dibenzo-5,12-diaza-1,8-dioxacyclotetradecan(2) in guter Ausbeute. Der makrozyklische Ligand 2,3:9,10-Dibenzo-5,12-diaza-1,8-dioxacyclotetradecan-N,N′-diessigsaure(3) wurde synthetisiert und analysiert. Die Reaktion von 2 mit einem Uberschus von Acrylnitril ergibt 2,3:9,10-Dibenzo-5,12-diaza-1,8-dioxacyclotetradecan-N,N′-di(2-cyanethyl) (4). Verschiedene Komplexe von diesen Liganden mit NiII, CuII und CoII wurden dargestellt und untersucht. Die Strukturen dieser Komplexe werden auf Grund von elementaranalytischen Daten, 1H, 13C-NMR, IR-, UV-VIS, magnetischen- und Leitfahigkeitsdaten vorgeschlagen.

Dibenzo[e,k]-2,3-bis(hydroxyimino) 1.4.7.10-tetrathia-2,3,8,9-tetrahydrocyclododecine (S4H2) and dibenzo-[e,k]-2,3-bis(hydroxyimino)-1,4-dithia-7,10-dioxa-2,3,8,9- tetrahydrocyclododecine (O2S2H2) have been prepared from (E,E)-dichloroglyoxime, 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane (DTT) and 2,3,8,9-Dibenzo-4,7-dioxa-1,10-dithiadecane (DDD) which was synthesized by treating 1,2-bis(o-aminophenoxy)ethane with HNO2 and potassium ethylxsanthate. The structures of these vic-dioximes have been determined as the (E,E)-forms according to 1H-NMR and IR data. Only mononuclear complexes with a metal-ligand ratio of 1:2 have been isolated with Co(II), such as [(S4H)2Co(III)L′Cl] and [(O2S2H)2Co(III)L′Cl]; Cu(II) forms only trinuclear complexes. Reaction of the mononuclear complexes with Pd(II) gives heterotrinuclear complexes.

Two-armed poly(epsilon-caprolactone) (TAPCL) polymers were successfully synthesized via the ring opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) using the Schiff's base complexes [Cu(SAEE)(2)] (1) and [Ni(SAEE)(2)] (2), which have two hydroxyl functional groups, as the two-site initiators and tin(II) 2-ethylhexanoate (Sn(Oct)(2)) as the catalyst in bulk at 115 degrees C. The Schiff's base complexes (1 and 2) were synthesized by utilizing the concentrated template synthesis method starting from salicyl aldehyde, 2-(2-aminoethoxy) ethanol and related metal acetate salts. The synthesized TAPCL polymers were characterized by GPC, FTIR, UV-vis, and electron paramagnetic resonance (EPR). The molecular weights of TAPCL polymers linearly increased with increasing molar ratio of the monomer to the initiator. The results obtained from FTIR, UV-vis, and EPR studies indicated that TAPCL polymers had the Schiff's base complexes at the junction point of PCL arms. The crystallization behavior of TAPCL was studied by using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Thermal behavior of TAPCL was also investigated by thermogravimetrical analysis (TGA). (C) 2010 Elsevier B.V. All rights reserved.

A new vicinal dioxiroe ligand with two 2-benzimidazolylmethyl groups, namely S,S′-bis(2-benzimidazolylroethyl)dithioglyoxime (H2L), has been prepared from cyanogen-di-N-oxide and 2-mercaptomethylbenz-imidazole in dichloromethane at -10°C. Nickel(II), palladium(II), cobalt(II) and cobalt(III) complexes of H2L have a metal : ligand ratio of 1 : 2 and the ligand coordinates through the two N atoms, as most of the vicinal dioximes. [Co(HL)2(L′)Cl] has been prepared with L′ = pyridine, 2,6-dimethylpyridine, 2-mercaptopyridine, 2-car-boxypyridine, pyridine-2-carboxyaldehyde, triphenylphosphine, tri-phenylarsine, together with a chloride ion as axial ligands. All these complexes are slightly soluble in common organic solvents. Structures are proposed according to elemental analyses, 1H, 13C-NMR IR, and UV-Visible spectral data.

A vicinal dioxime ligand with two 2-benzimidazolylmethyl groups, namely S,S'-bis(2-benzimidazolylmethyl) dithioglyoxine (H2L) and its axially pyridine and 2,6-dimethyl pyridine bonded Co(III) complexes were prepared according to prior literature [Y. Gok, S.Z. Yildiz, Synth. React. Inorg. Met-Org. Chem. 22 (9) (1992) 1327]. BF2+ bridged Co(111) complexes have been synthesized via the hydrogen-bridged Co(111) complexes by using borontrifloride ethyl ether complex. Heterotrinuclear complexes have been prepared by the reaction of these more soluble BF2-capped Co(III) complexes with stoichiometric amount of CdCl2 center dot H2O and NiCl2 center dot 6H(2)O salts. Using H-1, C-13 NMR, IR and MS spectral data and elemental analysis, the structures of the complexes were identified. Qualitative and quantitative determination of Co, Ni and Cd contents of the heterotrinuclear complexes have been investigated by energy dispersive X-ray fluorescence (EDXRF) method. An annular 50 mCi(241) Am radioactive source emitting 59.543 keV photons was used for excitation and Si(Li) detector having 157 eV FWHM at 5.9 keV was used for intensity measurements. (C) 2007 Elsevier B.V. All rights reserved.

It is known that 1,3-bis(benzo-15-crown-5)-2-thioxo-4,5-bis(hydroxyimino) imidazoline (H2L) exists in two isomeric forms which are amphi− and anti. The isomers differ by the orientations of OH and C=N groups on their oxime compounds. In the present work, the temperature dependance of the interconcersion of the amphi− vic−dioxime to anti− dioxime is investigated. The template effect on isomerisation is also studied. The every steps of geometric isomerizations are investigated with 1H, 13C-NMR and IR spectroscopy.