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The substituted phthalonitriles have been used to prepare soluble phthalocyanine species in recent years. One of the most used phthalonitrile derivatives for the target product is 4-nitrophthalonitrile. In this study 4-(4-formylphenoxy) phthalonitrile was prepared as the substituted phthalonitrile derivative by the nucleophilic substitution reaction of para-hydroxybenzaldehyde with 4-nitrophthalonitrile. During the crystallization of the product by slow evaporation technique, it readily self-oxidized to 4-(4-carboxylphenoxy) phthalonitrile at ambient condition open to air. The crystal structure of the molecule was determined by XRD technique. The molecule crystalizes at triclinic space group P-1 and the unit cell parameters of crystal are a6.3591 (10) Å, b7.5464 (11) Å, c13.819 (2) Å, ?88.434 (11), ?87.942 (12), ?80.111 (12) and Z2. The crystal structure has intermolecular O?HO, C?HN and C?HO hydrogen bonds. In addition to these hydrogen bonds, C—NCg and CgCg interactions are present between molecules. In the crystal, intermolecular O?HO hydrogen bonds occur between molecular units in a dimeric molecular form. Molecular structure, vibrational frequencies and 1H and 13C NMR chemical shifts of the target compound have been calculated by using B3LYP method with 6-311G(d, p) basis set, as well. Sübstitüe ftalonitriller, son yıllarda çözünür ftalosiyanin türlerini hazırlamak için kullanılmaktadır. Hedef ürün için en çok kullanılan ftalonitril türevlerinden biri, 4-nitroftalonitrildir. Bu çalışmada, 4-(4-formilfenoksi) ftalonitril, para-hidroksibenzaldehidin 4-nitroftalonitril ile nükleofilik yerdeğiştirme reaksiyonu ile sübstitüe ftalonitril türevi olarak hazırlanmıştır. Ürün yavaş buharlaştırma tekniği ile kristallendirilmesi sırasında, havaya açık ortam koşullarında, 4- (4-karboksilfenoksi) ftalonitril'e kendiliğinden oksitlenmiştir. Molekülün kristal yapısı XRD tekniği ile belirlendi. Molekül, triklinik uzay grubu P-1'de kristallenmiştir ve kristalin birim hücre parametreleri a 6.3591 (10) Å, b 7.5464 (11) Å, c 13.819 (2) Å, a 88.434 (11) , 87 87.942 (12) , ? 80.111 (12) ve Z 2’ dir. Kristal yapı moleküllerarası O ? H O, C ? H N ve C ? H O hidrojen bağlarına sahiptir. Bu hidrojen bağlarına ek olarak, moleküller arasında C — N Cg ve Cg Cg etkileşimleri mevcuttur. Kristalde moleküllerarası O ? H O hidrojen bağları, bir dimerik yapı içinde moleküler birimler arasında meydana gelir. Hedef bileşiğin, moleküler yapısı, titreşim frekansları ve 1H ve 13C NMR kimyasal kaymaları da 6-311 G (d, p) temel seti ile B3LYP metodu kullanılarak hesaplanmıştır.

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) (2), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) (3) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) (4) as tri-nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2, 3, 4 was performed through the reaction of a Schiff base-substituted phthalocyanine using MnCl(2)4H(2)O, CoCl(2)6H(2)O or FeCl(3)6H(2)O salts in basic condition in dimethylformamide. Fourier transform infrared, H-1 NMR, C-13 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 2, 3, 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2, 3, 4/H2O2 combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2, 3, 4 exhibited better bleaching performance at 25 degrees C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright (c) 2015 John Wiley & Sons, Ltd.

kanmazalp, sibel demir/0000-0002-5896-0966; Dege, Necmi/0000-0003-0660-4721; Ozdemir, Namik/0000-0003-3371-9874; Sen, Pinar/0000-0002-3181-9890 WOS: 000477632400016 PubMed: 31391965 This work presents the synthesis and structural characterization of [4-(1H-benzo[d]imidazol-2-yl) phenoxy]phthalonitrile, a phthalonitrile derivative carrying a benzimidazole moiety. The compound crystallizes as its dimethyl sulfoxide monosolvate, C21H12N4O center dot(CH3)(2)SO. The dihedral angle between the two fused rings in the heterocyclic ring system is 2.11 (1)degrees, while the phenyl ring attached to the imidazole moiety is inclined by 20.7 (1)degrees to the latter. In the crystal structure, adjacent molecules are connected by pairs of weak intermolecular C-H center dot center dot center dot N hydrogen bonds into inversion dimers. N-H center dot center dot center dot O and C-H center dot center dot center dot O hydrogen bonds with R-2(1)(7) graph-set motifs are also formed between the organic molecule and the disordered dimethyl sulfoxide solvent [occupancy ratio of 0.623 (5):0.377 (5) for the two sites of the sulfur atom]. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state. Ondokuz Mayis UniversityOndokuz Mayis University [PYOFEN.1906.19.001] This study was supported by Ondokuz Mayis University under project No. PYOFEN.1906.19.001 (contract No. PYOFEN.1906.19.001).

Dege, Necmi/0000-0003-0660-4721; kanmazalp, sibel demir/0000-0002-5896-0966 WOS: 000477950400008 This work presents the synthesis and characterization of a novel compound, 4-(2-(2-(2-formylphenoxy)ethoxy)ethoxylphthalonitrile as the aldehyde functional group substituted as a phthalonitrile derivative. The spectroscopic properties of the compound were examined through Fourier-transform infrared spectroscopy, Proton nuclear magnetic resonance, Carbon nuclear magnetic resonance, Ultraviolet-visible spectroscopy, Mass spectrometry and elemental analyses. The molecular structure of the compound was also confirmed using X-ray single-crystal data with a theoretical comparative approach. Research Fund of Sakarya UniversitySakarya University [2014-02-04 007] This work was supported by the Research Fund of Sakarya University (project no. 2014-02-04 007).

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.

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.

Bu çalışmada şelat yapılı metal-imin kompleksleri sentezlendi ve hava kurumalı boya sistemlerindeki kurutucu katalitik etkileri konvansiyonel tipteki boya kurutucuları ile kıyaslandı. Hazırlanan şelat ligandın ilgili geçiş metali kompleksleri, 1. sıra geçiş metal tuzlarıyla, solvent ve karboksilik asit içerisinde sentezlendi. Komplekslerin hazırlanmasında Co(II), Mn(II) ve Fe(III) tuzları kullanıldı. Hazırlanan imin yapılı ligandın karakterizasyonu 1H-NMR, 13C-NMR, FT-IR spektroskopi teknikleri ve elemental analiz ile gerçekleştirildi. Hazırlanan ligand ve ilgili uzun zincirli karboksilik asitlerden hareketle sentezlenen meta-şelat yapılı Co3+, Mn3+ ve Fe3+ imin-karboksilat komplekslerinin karakterizasyonların da ise FT-IR, Elemental Analiz, Uv-Vis ve MS spektroskopisi metotları kullanıldı. Birer oksidasyon katalizörü niteliğindeki bu Şelat yapılı metal-imin karboksilat ürünlerinin boya performans testleri ASTM D5895'e göre BK kuruma süresi kaydedici cihazında ölçüldü. Elde edilen değerler ticari olarak kullanılmakta olan kurutucu katalizör türleri ile karşılaştırmalı olarak değerlendirildi.Elde ettiğimiz Co3+, Mn3+ ve Fe3+ imin kompleksleri piyasada bulunan standart boya kurutucular ile kıyaslandığında ve özellikle kobaltın kullanılmasının kısıtlandığı boya formülasyonları açısından ümit verici başarılı sonuçlar kaydedildi. In this study chelate structured metal-imine complexes were synthesized and the desiccant catalytic effects of air-dried paint systems were compared with conventional type paint dryers. The respective transition metal complexes of the prepared chelate ligand were synthesized in the first order transition metal salts, solvent and carboxylic acid. Co(II), Mn(II) and Fe(III) salts were used in the preparation of the complexes.The characterization of the prepared imine ligand was carried out by 1H-NMR, 13C-NMR, FT-IR spectroscopy techniques and elemental analysis. FT-IR, Elemental Analysis, Uv-Vis and MS spectroscopy methods were used for characterization of the meta-chelate Co3 +, Mn3 + and Fe3 + imine-carboxylate complexes synthesized from the prepared ligand and related long chain carboxylic acids. The paint performance tests of these chelate structured metal-imine carboxylate products, which are the oxidation catalysts, were measured in the BK drying time recorder according to ASTM D5895. The values obtained were evaluated as comparative with the commercially available drying catalyst types.The obtained Co3+, Mn3+ and Fe3+ imine complexes were compared with the standard paint dryers found on the market and successful results were obtained in the paint formulations, especially in which the use of cobalt was restricted. 92

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.

Zwitter ionic macro molecules can be prepared to provide functional materials applicable in various different fields such as catalysis, cleaning industry, textile industry, cosmetics and drugs with the enhanced solubility both in organic solvent and aqueous media. Tetra {4-[N-((3-dimethylamino)propyl) amidelphenoxyl substituted nickel (II) phthalocyanine (2) and its sulfobetaine, betaine, and N-Oxide derivatives (3-5) were synthesized as novel species. All newly synthesized compounds (1-5) were characterized by the combination of spectroscopic techniques such as UV Vis, FT-IR, H-1 NMR, C-13 NMR, mass and elemental analysis, as well. The ionic phthalocyanine derivatives (3-5) showed excellent solubility in aqueous media due to their ionic characters. In this study, antioxidant capacities of the phthalonitrile (1) and phthalocyanines (2-5) were tested via radical scavenging methods; 2,2-diphenyl1-picrylhydrazyl free radical (DPPH") scavenging, 2,2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, and cupric reducing antioxidant capacity (CUPRAC) method. In addition to this radical scavenging studies, reducing power activity of compounds (1-5) were tested as well. Surfactant properties of ionic derivatives (3-5) were also investigated in water. Results revealed that all the synthesized compounds have antioxidant activity (1-5) and water soluble phthalocyanines (3-5) have good surfactant properties, as well. (C) 2016 Elsevier B.V. All rights reserved.

In this study, the novel water soluble derivatives of 2-[N-((3-morpholino)propyl)carbamate]oxyethyl substituted zinc(II) phthalocyanine (1) bearing different type of groups such as sulfobetaine (2), betaine (3), N-Oxide (4) and quaternized methyl (5) on the morpholine core were synthesized for the first time. All newly synthesized zinc(II) phthalocyanine derivatives were characterized by different spectroscopic techniques such as UV-vis, FT-IR, H-1 NMR, mass and elemental analysis as well. They showed excellent solubility in aqueous media due to their zwitterionic and ionic characters which makes them promising candidates for treatment of cancer by photodynamic therapy (PDT). The photophysical and photochemical properties were investigated in DMSO for tetrakis(2-[N-((3-morpholino)propyl)carbamate]oxyethyl} substituted zinc(II) phthalocyanine (1) and in both DMSO and water+Triton X-100 solutions for its water soluble ionic derivatives (2-5). The binding behaviors of ionic zinc(II) phthalocyanines by bovine serum albumin (BSA) protein were investigated for determination of transportation ability of these phthalocyanines in the blood circulation. (C) 2016 Elsevier B.V. All rights reserved.

In this study, 4-{4-[N-((3-dimethylamino)propyl)amide]phenoxy}phthalonitrile (1) and its zinc(II) phthalocyanine derivative (2) were synthesized for the first time. 4-(N-((3-Dimethylamino)propyl)amide)phenoxy substituted zinc(II) phthalocyanine (2) was converted to its water-soluble sulfobetaine (3), betaine (4) and N-oxide (5) containing zwitterionic and quaternized cationic (6) derivatives. All newly synthesized compounds (1-6) were characterized by the combination of UV-vis, FT-IR, H-1 NMR, mass spectroscopy techniques and elemental analysis. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen quantum yields) properties were investigated in DMSO for all the synthesized zinc(II) phthalocyanines (2-6) and in both DMSO and aqueous solutions for zwitterionic and cationic phthalocyanines (3-6) for the specification of their capability as photosensitizers in photodynamic therapy (PDT). The binding behavior of water soluble phthalocyanines (3-6) to the bovine serum albumin protein was also examined for the determination of their transportation ability in the blood stream.

Kimyasal proseslerde elde edilen ürünün verimini ya da kalitesini yükseltmekamacıyla bir yardımcı bileşene ihtiyaç duyulur. Bu nedenle reaksiyonların hızınıarttırmak ya da elde edilmek istenen ürünün yan ürünlere göre daha çok eldeedilmesini sağlayan maddeler kullanılır. Genellikle kullanılan maddeler katalizörlerolup, rekasiyonlarda verimlilik ve seçicilik yönünden, kimya alanında endüstriyelaçıdan en önemli nitelik olarak yer almaktadırlar. Katalizörler, yüksek verim veseçicilik gibi oluşturulması istenilen ürünün korunması ve saf halde edilmesini içinyardımcı olur. Reaksiyonlar için enerji ve madde gereksinimini azaltarak yüksekverimlerin elde edilmesini sağlar. Katalizörler aktivite, reaksiyon ömrü, yeniden eldeedilebilirlik ve seçicilik gibi elde edilmesi istenen değerlere ortam sağlar. İçerisindeyer alan sanayinin gelişmesi açısından önemli bir rolü vardır.Aldehitlerin asitlere oksidasyon reaksiyonları kimya sanayi açısından çok tercih edilenve çalışılan reaksiyonlardır. Bu nedenden dolayı reaksiyonlar için bir dizi reaktanlarveya katalizörler söz konusudur. İçlerinden bazıları farklı reaksiyonlara uygulanabilir.Bu nedenden dolayı sodyumklorit aldehitlerin asitlere yükseltgenmesireaksiyonlarında düşük pH değerlerinde yüksek verimle çalışan reaktant olarakbulunmuştur.Bu çalışmada oksidant olarak klordioksit üretmek veya etkinliğini artırmak için farklıkatalizörler kullanarak benzaldehitin benzoik asite yükseltgeme şartlarınınaraştırılması yapıldı. Sodyumklorit ve stabilize klordioksit çözeltisi reaktant olarakkullanıldı. NaH2PO4, KMnO4, V2O5, 1-Hidroksi Etilidin-1,1-Difosfonik Asit (HEDP),Sodyum Tripolifosfat (STPP)/Formik Asit ve hazırlanan farklı Mn ve Co komplekslerikatalizör olarak kullanıldı. Her katalizör için farklı pH değerlerine göre araştırmalaryapılarak verim karşılaştırmaları yapıldı. En yüksek verimler metal komplekslerininkatalizör olarak kullanıldığı çalışmalarda elde edildi. Çalışma şartlarına göre dahayüksek pH' larda yapılan çalışmalarda verimlerin düşük olduğu, ancak pH' ların asidiktarafa kaydığı çalışmalarda verimlerin giderek arttığı gözlenmiştir. Metal katalizörlerikullanıldığı çalışmalarda oksidasyon verimlerinin pH 6 nın üzerinde ki değerlerde%83 lerin üzerine çıkarılabileceği tespit edildi. A number of chemical products require an auxiliary material to increase the yield andquality of the final product. To this purpose, substances which accelerate the reactionsand increase the generation of the desired product relative to by-products have beenused. These materials, which are called catalysts, are essential industrial materials ofchemical industry in terms of productivity and austerity of catalysts manifacture;preservation of the raw material and reduction of impurities ensure high selectivity andproductivity. Chemical reactions reduce raw material and energy requirements. Inorder for a catalyst to be useful, it must be at the desired values in terms of activity,selectivity, service life and renewability. Development of catalyst technology is vitalfor the development of chemical industry.Acid oxidation of aldehydes is a reaction that has been studied extensively due to theirindustrial significance. For this purpose, a number of reactants to are mentioned inliterature. However, some of these can be tolerated and applicable different types ofaldehydes. Sodium chloride has been discovered as a reactant that operates undermoderate conditions in acidic oxidation of aldehydes.In this study, to produce chlorodioxide as an oxidant or to ensure its effectiveness byusing catalyst, benzaldehyde benzoic acid oxidation conditions have been investigated.Sodium chloride and stabilized chlorine dioxide solution were used as reactants.NaH2PO4, KMnO4, V2O5, 1-Hydroxyethylidine-1,1-Diphosphonic Acid (HEDP),Sodium Tripolyphosphate (STPP) / Formic Acid and the different Mn and Cocomplexes prepared were used as catalysts. For each catalyst, the yields werecompared according to different pH values. The highest yields were obtained whenmetal complexes were used as catalysts. It was observed that at high pHs the yieldsdecreased, despite that when pHs were acidic the yields started to gradually increaseagain. It has been found that the oxidation efficiencies of metal catalysts can beincreased to over 83% above pH 6. 89

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).

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).

In the present study, polyamine polyurea polymer was employed for adsorption of Cr(VI) ions from aqueous solution. Adsorption studies were carried out to examine the effects of parameters such as pH, contact time, initial concentration of Cr(VI), and temperature. Optimum pH value and the contact time of the system were found to be 2.5 and 240 minutes, respectively. Thermodynamic parameters that calculated with the results of temperature studies showed the adsorption processes have exothermic, reversible, and spontaneous nature. The compared isotherm data clarified that Cr(VI) adsorption onto polyamine polyurea polymer (PPP) was proper with Langmuir isotherm with maximum adsorption capacity of 135.1 mg g(-1). Pseudo-second-order kinetic model was found to be descriptive for the kinetic mechanism of Cr(VI) adsorption onto PPP. Single-stage batch adsorber was designed using equilibrium data for removal of Cr(VI) at various solutions. Consequently, the PPP has been found to be effective adsorbent for removal of Cr(VI) from water media.

Silica gelwas functionalized with N-(2-aminoethyl)-2,3-dihydroxybenzaldimine group (AEDHB-SG) and characterized by elemental analysis and FT-IR spectroscopy. Preconcentration conditions of Cd(II), Cu(II), Ni(II) and Pb(II) were investigated on the AEDHB-SG loaded column using a solid phase extraction technique. The effects of parameters such as the pH, sample volume, flow rates, matrix ions were examined. Adsorption capacity of AEDHB-SG for Cd(II), Cu(II), Ni(II) and Pb(II) was 0.40, 0.56, 0.50 and 0.23 mmol g(-1). The accuracy of the developed method was confirmed by certified reference materials. Optimized method was applied to water and food samples for the determination of trace metals using ICP-OES. (C) 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

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).

06.03.2018 tarihli ve 30352 sayılı Resmi Gazetede yayımlanan “Yükseköğretim Kanunu İle Bazı Kanun Ve Kanun Hükmünde Kararnamelerde Değişiklik Yapılması Hakkında Kanun” ile 18.06.2018 tarihli “Lisansüstü Tezlerin Elektronik Ortamda Toplanması, Düzenlenmesi ve Erişime Açılmasına İlişkin Yönerge” gereğince tam metin erişime açılmıştır. Bu çalışmada makrosiklik Schiff bazı sentezi gerçekleştirildi. Bu ligandın ilgili geçiş metali kompleksleri 1. sıra geçiş metal tuzlarıyla etanolik çözeltiler içinde sentezlendi. Komplekslerin hazırlanmasında CoCl2.6H2O, MnCl2.6H2O, FeCl3 ve ZnCl2 tuzları kullanıldı. Hazırlanan makrosiklik Schiff bazının karakterizasyonu 1H-NMR, 13C-NMR, FT-IR, elemental analiz, UV-Vis. ve MS spektroskopi teknikleri ile gerçekleştirildi. Hazırlanan Co3+, Mn3+, Fe3+ ve Zn+2 komplekslerinin karakterizasyonların da ise FT-IR, Elemental Analiz, Uv-Vis, Floresans spektroskopi ve MS spektroskopi metotları kullanıldı. Oksidasyon reaksiyonları, doğal kırmızı meyvelerin boyasını karakterize eden üzere poli hidroksi fenolik boya olarak Morin kullanılarak online-spektroskopik metod ile gerçekleştirildi. Ölçümler pH 10.5'de tampon çözeltisi ve deterjan baz çözeltisi ortamında H2O2 oksidanı eşliğinde hazırlanan katalizör örnekleri ile yapıldı. Katalizör olarak sentezlenen Schiff bazı kompleksleri kullanıldı. Ağartma potansiyelinin ölçülmesinde UV-Vis spektrumlarında Morinin 411 nm'deki maksimum absorbansının zamanla azalması gözlemlendi. Sonuçlar % ağarma değerleri olarak zamana karşı grafiğe geçirildi ve değerlendirildi. Yapılan çalışmalarda bi-metalik (bi-nükleer, iki çekirdekli) Schiff bazı içeren makrosiklik yapılı oksidasyon katalizörleri hazırlandı. Hazırlanan bu katalizörler yüksek ağartma etkinliği gösterdi. Bu katalizörler ağartma katalizörleri olarak aday katalizör olmaktadır. Sentezlenen katalizörlerin DMSO ve DMF' de 1x10-5 M'de konsantrasyonda çözeltileri hazırlandı. Hazırlanan bu çözeltilerin floresans spektroskopisinde floresans karakterleri ölçüldü. Uyarma ve emisyon spektrumlarının yoğunluğa karşı dalgaboyu grafikleri çizildi. Elde edilen spektrumlardan Stokes kayması belirlendi. Zn+2 iyonların her iki çözeltide emisyon verimini artırdığı gözlemlenirken, diğer paramanyetik metal iyonlarını ise floresans quantum verimini sönümlendirdiği gözlemlendi. In this study, Schiff base type ligand was synthesized. The metal complexes were synthesized from the prepared ligand in ethanol by using related transition metal salts, such as CoCl2.6H2O6, MnCl2.6H2O6, FeCl3 and ZnCl2. Synthesized Schiff base ligand was characterized by 1H-NMR, 13C-NMR, FT-IR, Elemental Analysis, Uv-Vis and MS spectroscopy techniques. The prepared Co3+, Mn3+, Fe3+ ve Zn+2 complexes were also characterized by FT-IR, Elemental Analysis, Uv-Vis, fluorescence spectroscopy and MS spectroscopy methods. Oxidation reactions were carried out by online spectroscopic methods using Morin as natural polyhydroxy phenolic dye to characterize the natural red fruits' dye. Measurements were carried out for the samples prepared as the catalyst in the presence of H2O2 at a buffer solution and detergent base solution formed in the of 10.5 pH. The prepared Schiff base complexes were used as the catalysts. The measumerement of bleaching kinetics on UV- Vis. It was observed that the maximum absorbance of morinin at 411 nm decreased with time. The results were plotted against time as percent bleaching values. During the studies, macrocyclic oxidation catalysts, containing bi-metallic (bi-nuclear, bi nuclear) Schiff base, were prepared. The prepared catalysts showed high bleaching activity. These catalysts are candidate catalysts the bleach catalysts. Solutions of the synthesized catalysts were prepared at 1x10-5 M concentrations in DMSO and DMF. The fluorescence properties of these solutions were measured by fluorescence spectroscopy. Wavelet graps were plotted against the intensity of the excitation and emission spectra. Stokes shift was determined from the obtained spectra. It was observed that Zn+2 ions increased the emission efficiency in both solutions while other paramagnetic metal ions attenuated the fluorescence quantum yield.

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).

Bu tez çalışması kapsamında, deterjan uygulamalarında ağartma katalizörü olarak kullanılabilecek fonksiyonel ftalosiyaninler sentezlenmiş ve katalitik etkinlikleri araştırılmıştır.Ftalosiyaninler, yüksek stabilite, yapısal esneklik, çeşitli koordinasyon özellikleri, mükemmel spektroskopik özellikleri ve zengin redoks kimyası nedeniyle, ilginç endüstriyel uygulamalar için bilinen N4-makrosiklik bileşiklerdir. Periyodik tablonun d-blok metallerini ihtiva eden ftalosiyaninler, olefinlerin, alkollerin, aromatik maddelerin ve diğer bazı bileşiklerin katalitik oksidasyonlarında etkili bir katalizör olarak yaygın olarak kullanılmaktadır. Schiff bazları, çoğu geçiş metali ile kompleks oluşturabildiğinden, koordinasyon kimyasının gelişiminde önemli rol oynamıştır. Bu bileşiklerin üstün katalitik özelliklerinden dolayı yeni moleküler malzemelerin oluşturulması yönünde çalışmalar yoğunlaşmaktadır.Bunun için tezin ilk aşaması, Co(III), Mn(III), Fe(III) iyonlarını içeren Schiff bazı metal komplekslerinin doğrudan oksijen köprüleri yoluyla Pc çekirdeğine bağlanmasıyla elde edilen ftalosiyaninleri (8-10, 16-18, 22-24) ve aynı amaçla Co(II) ve Mn(II) terpiridin komplekslerini taşıyan ftalosiyaninleri (33-34) içermektedir. İkinci aşamada, mangan merkez atomu içeren nötr (34-36) ve katyonik (37) ftalosiyaninler, sonraki aşamada demir ve kobalt merkez atomlarını içeren nötr (38-39) ve kafes tipi (40-41) ftalosiyaninler, son aşamada ise kobalt ve mangan merkez atomu içeren benzimidazol substitue ftalosiyaninler (44-45, 47-48) elde edilmiştir. Elde edilen bu dört farklı sınıf ftalosiyanin bileşiklerinin karakterizasyonu, erime noktası, elementel analiz, FT-IR, 1H-NMR, 13C-NMR, UV-Vis, ICP-OES ve kütle (MALDI-TOF) spektral verileri ile yapılmıştır. Elde edilen moleküllerin ağartma katalizörü olarak performansları, spektrofotometrik yöntem kullanılarak incelenmiştir. Hazırlanan katalizörlerin, toz deterjan formülasyonlarında ticari olarak kullanılan tetraasetiletilendiamin (TAED) ağartıcı aktivatöründen 25°C'de daha iyi ağartma performansı sergilediği bulunmuştur. Within the scope of this thesis, functional phthalocyanines, which can be used as bleaching catalysts in detergent applications, have been synthesized and catalytic activities have been investigated.Phthalocyanines are a kind of N4-macrocycles known for their very interesting industrial applications due to their high stability, structural flexibility, diverse coordination properties, excellent spectroscopic characteristics, and rich redox chemistry. Phthalocyanines containing d-block metals of the periodic table are widely used as efficient catalyst in the catalytic oxidations of olefins, alcohols, aromatics and some other compounds. Schiff bases play an important role in the development of coordination chemistry, as they can form complexes with many transition metals. Due to the superior catalytic properties of these compounds, the work towards the formation of new molecular materials is intensified.The first stage of the thesis contains the phthalocyanines (8-10, 16-18, 22-24) obtained by coupling Schiff base metal complexes containing Co (III), Mn (III), and Fe (III) ions directly bonded to Pc core via oxygen bridges and the phthalocyanines (33-34) carrying Co (II) and Mn (II) terpyridine complexes for the same purpose. In the second stage, neutral (34-36) and cationic (37) phthalocyanines containing manganese center atom, the neutral (38-39) and cage-type (40-41) phthalocyanines containing iron and cobalt center atoms, respectively in the next stage. In the last stage, benzimidazole substituted phthalocyanines (44-45, 47-48) containing cobalt and manganese center atom were obtained. The characterization of these four classes of phthalocyanine compounds was made by means of melting point, elemental analysis, FT-IR, 1H-NMR, 13C-NMR, UV-Vis, ICP-OES and mass (MALDI-TOF) spectral data. The performance of the obtained molecules as bleach catalysts was investigated by spectrophotometric method. 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. 322

The synthesis of tetraaminopropylamid substituted phthalocyanines was targeted to prepare enhanced soluble phthalocyanines in common solvents from hydrophobic to hydrophilic that bore nonionic groups on their periphery. Metal-free (H2Pc) and metallophthalocyanines (Zn(II) (ZnPc), Cu(II) (CuPc) and Co(II) (CoPc)) were prepared and characterized by UV-Vis, FT-IR, and mass spectroscopies. The H-1 NMR spectra were recorded for the diamagnetic phthalocyanine species H2Pc and ZnPc. The phthalocyanines showed sufficient solubility in common organic solvents such as dimethyl sulfoxide, tetrahydrofuran, and ethanol. However, methanol was not a good solvent for CuPc and H2Pc. Solubility and aggregation studies of H2Pc and ZnPc were performed in different solvents and different concentrations in DMF. The solubility in water was also examined by altering pH to exhibit solubility characteristic in polar solvents for H2Pc and ZnPc.

In this study, a Cd(II) complex was synthesized using 8-hydroxyquinoline and thiocyanate as the ligands and structurally characterized with the combination of FTIR, H-1-NMR, C-13-NMR, UV-vis, and MS spectral data. Then, genotoxic effects of the prepared complex were investigated. Genotoxic properties of the dimeric 8-hydroxyquinolinthiocyanatoCd(II) [Cd-2(8Q)(2)(SCN)(2)] complex synthesized as drug raw material were analyzed in human peripheral blood lymphocytes. Concentrations of 1, 2, 4, 6, and 8g/mL [Cd-2(8Q)(2)(SCN)(2)] were used for 24 and 48 h durations. [Cd-2(8Q)(2)(SCN)(2)] significantly increased chromosomal aberrations (CAs) at 4, 6, and 8g/mL concentrations after a 24-h period and 2 and 4g/mL after a 48-h period. [Cd-2(8Q)(2)(SCN)(2)] significantly decreased the mitotic index (MI) at all concentrations, both at 24 and 48h. Micronuclei frequency (MN) was not affected by [Cd-2(8Q)(2)(SCN)(2)] treatment compared with the control. After application for a 48h period, 6 and 8 mu g/mL concentrations showed toxic effects both in chromosomal abnormality and in micronucleus tests. It also decreased the cytokinesis-block proliferation index (CBPI), but this result was statistically significant only at 6 and 8 mu g/mL concentrations. In the comet assay (single-cell gel electrophoresis (SCGE)), significant increases in comet tail length, tail moment, and tail intensity were observed at all concentrations. [Cd-2(8Q)(2)(SCN)(2)] displays clastogenic effect in the concentrations used in human peripheral lymphocytes at chromosomal abnormality, micronucleus tests, and cytokinesis-block proliferation index parameters. Further studies should be conducted in other test systems to evaluate the complete genotoxic potential of [Cd-2(8Q)(2)(SCN)(2)].

Hazelnut husk, an agricultural waste, was used to prepare an activated carbon (HHPCAC) by chemical activation using K2CO3. HHPCAC was characterized by FT-IR spectroscopy, BET surface area determination, SEM, Boehm titration, proximate, and elemental analysis. HHPCAC has a high surface area (980.9m(2)g(-1)) and contains 2.60mmolg(-1) of total acidic functional groups. HHPCAC was used for the removal of Pb(II) from aqueous solutions by investigating a number of effective factors such as initial pH, contact time, dosage, and initial concentration. Adsorption of Pb(II) ions is highly dependent on pH of the solution, and its optimal value was found to be 5.0. Time to equilibrium was found as 20h. Kinetics of Pb(II) adsorption on HHPCAC followed pseudo-second-order model. Adsorption equilibrium data were analyzed by Langmuir and Freundlich models. Maximum adsorption capacity of HHPCAC for Pb(II) was calculated as 109.9mgg(-1) using Langmuir equation. From the findings, it could be concluded that HHPCAC is a feasible adsorbent for the removal of Pb(II) ions from aqueous solutions.

In this study, polyamine-polyurea polymer was synthesized using toluendiisocyanate and polyethyleneimine. It was then modified using pyromellitic dianhydride. The polymer so obtained (PMPPP) was used for the adsorption of Cd(II) metal ions from aqueous solutions using a batch adsorption system to simulate the adsorption characteristics of wastewater applications. The effects of pH, dosage, contact time, initial concentration, and temperature were investigated. The optimum pH value was found to be 6.0, and the contact time required to reach equilibrium was 120min. The Cd(II) adsorption equilibrium data were found to be more in line with the Langmuir equation than the Freundlich model. The maximum adsorption capacity of PMPPP for Cd(II) was calculated to be 94.3mgg(-1). Kinetics studies showed that Cd(II) adsorption followed the pseudo-second-order equation. Thermodynamic investigations revealed endothermicity, spontaneity, and an increased randomness of Cd(II) adsorption onto PMPPP. Polymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric-differential thermal analysis, scanning electron microscopy, and nitrogen adsorption/desorption isotherms.

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.

Kara, Derya (Balikesir Author), Silica gel functionalized with 2-[N,N'-bis(2,3-dihydroxybenzaldimin)] aminoethylamine was employed as a novel sorbent for preconcentration of copper(II), cobalt(II), and cadmium(II) by flow injection-solid phase extraction. The pH of the analyte solution, sample and eluent flow rate, eluent volume, and the presence of concomitant ions were optimized. The limits of detection were 0.65, 0.52, and 1.42 mu g/L and preconcentration factors were 12.3, 21.5, and 7.31 for cadmium(II), copper(II), and cobalt(II), respectively. The adsorption capacities of the functionalized silica gel for cadmium(II), copper(II), and cobalt(II) ions were 41.1, 31.7, and 26.5mg/g. The preconcentration method was validated by determination of cadmium(II), copper(II), and cobalt(II) levels in Virginia Tobacco Leaves (CTA-VTL-2) and Water-Trace Elements (NWTM-15.2) certified reference materials. The method was also used to analyze water and food samples, and offers simplicity, reproducibility, high recovery, rapid and automated analysis, favorable ease of use, and low detection limits.

Bu çalışmada Schiff bazı yapılı N-2(2-hidroksietiloksi)etil-2,4-dihidroksi benzaldimin (2,4-DHBAEE), N-2(2-hidroksietiloksi)etil-2,3-dihidroksibenzaldimin (2,3-DHBAEE) ve N-2-hidroksietil-2,4-dihidroksibenzaldimin (2,4 DHBAE) metanolik çözelti içerisinde in-situ olarak hazırlanmış ve akabinde ilgili geçiş metal tuzlarının metanoldeki çözeltileri ilave edilerek kompleklerin sentezleri gerçekleştirilmiştir. Komplekslerin hazırlanmasında Cu(OAc)2, Ni(OAc)2, PdCl2 tuzları kullanıldı.Sentezlenen hidroksil fonksiyonel grubu içeren komplekslerden hareketle metal içeren epoksi polimerleri, diglisidil eter Bisfenol-A (DGEBA) ve katalizör olarak tetrabutil amonyumhidroksit (TBAH) kullanılarak hazırlandı. Kürleme şartları azot atmosferi altında 150 °C ve 175 °C de gerçekleştirildi. Hazırlanan Schiff bazı kompleklerinin karakterizasyonları erime noktası tayinleri, FT-IR ve MS spektroskopi teknikleri ile gerçekleştirildi. Hazırlanan Cu2+, Ni2+, Pd2+, komplekslerini içeren epoksi polimerlerinin karakterizasyonları FT-IR spektroskopisi ile gerçekleştirildi. Kinetik çalışmalar doğal kırmızı meyvelerin boyasını karakterize etmek üzere doğal polihidroksi fenolik boya olarak Morin kullanılarak online-spektroskopik metod ile gerçekleştirildi. Ölçümler pH 10-11 aralığında tampon çözelti ortamında H2O2 eşliğinde hazırlanan ilgili katalizör örnekleri ile gerçekleştirildi. Katalizör olarak sentezlenen Schiff bazı komplekleri ve bunlardan hareketle hazırlanan metal içeren epoksi polimerleri kullanıldı. Ağarma kinetiklerinin ölçülmesinde Uv-Vis. spektrumlarında 411 nm deki Morin absorbsiyonlarında zamanla oluşan azalma olarak gözlendi. Sonuçlar % ağarma değerleri olarak zamana karşı grafiğe geçirildi.Hazırlanan katalizör örneklerinden kompleklerin genel olarak polimerlerden daha hızlı ağartma kinetiğine sahip oldukları belirlendi. Hem polimerler için ve hem de komplekslerin ağartma hızları Cu(II)>Ni(II)>Pd(II) olarak verilebilir.Anahtar kelimeler: Schiff bazı, Schif Bazı Metal Kompleksi, Metal içeren epoksi polimerler, Katalizör In this study Schiff base complexes made of N-2(2-hyroxyethyloxy) ethyl-2,4-dihydroxy benzaldimine (2,4-DHBAEE), N-2(2-hyroxyethyloxy) ethyl-2,3-dihydroxy benzaldimine (2,3-DHBAEE) and N-2-hyroxyethyl-2,4-dihydroxybenzaldimine (2,4-DHBAE) as the ligands which were prepared as in-situ in the reaction solution and the related transition metal salts were prepared. The preparation of complexes was performend in methanol by using Cu(OAc)2, Ni(OAc)2, PdCl2 as the metal salts.Epoxy polymers containing transition complexes were synthesized via the prepared hydroxyl functional group included Schiff base complexes and diglycidyl ether bisphenol-A (DGEBA) using tetrabutyl ammonium hydroxide (TBAH) as the catalyst. Curing experiments were performed under a nitrogen atmosphere at 150°C and 175 °C. The characterization of the prepared Schiff base complexes were performed by the combination of melting point determinations, MS and FTIR spectroscopy techniques. However the characterization of the epoxy polymer containing Cu2+, Ni2+ and Pd2+complexes were performed with FT- IR spectroscopy.Kinetic studies were carried out by online spectroscopic methods using Morin as natural polyhydroxy phenolic dye to characterize the natural red fruits' dye. Measurements were carried out for the samples prepared as the catalyst in the presence of H2O2 at a buffer solution formed in the range of 10-11 pH. The prepared Schiff base complexes and the epoxy polymers which also contained metal motion were used as the catalysts. The measurement of bleaching kinetics on UV-Vis. spectra was followed by the decreasing of absorbences of Morin at 411 nm with time. The results were graphed as the values of bleaching % against time.In general, it was observed that the complexes had more rapid bleaching kinetics then the polymers. The observed bleache rate order can be given as Cu(II)> Ni (II)> Pd (II). 94

The metal-free phthalocyanine 2 was synthesized from the 4,5-bis(1,4,7,10-tetraoxacyclododecan-2-ylmethoxy)phthalonitrile 1 in the presence of a strong base in n-pentanol. The synthesis of metallo derivatives [Ni(II), Co(II), Cu(II)] of phthalocyanines obtained from corresponding phthalonitrile derivative 1 and in the presence of the anhydrous divalent metal salts (NiCl2, CoCl2 and CuCl2) were described. The thermal stabilities of the metal-free and metallophthalocyanines were determined by thermogravimetric analysis. These phthalocyanines were good soluble inorganic solvents such as chloroform, dichloromethane, tetrahydrofuran and DMF. The products were characterized by elemental analysis, IR, H-1 NMR, UV-vis and MS spectral data. (C) 2010 Elsevier B.V. All rights reserved.

Bu çalışma, yeni tip poli-fonksiyonel metal komplekslerinin sentezi, karakterizasyonu ve farklı monomerle polimerleşebilme şartlarının araştırılmasına dayanmaktadır. Sentezlenen poli -OH fonksiyonel komplekslerin, 1,4-toluendiizosiyanat varlığında üretan polimerlerine ve glisidil eter türevleri ile epoksi polimerlerine dönüştürülmesi şartları araştırılmıştır. Çalışmamızda sırası ile (E)-1-((2-(2-hidroksietoksi)etilimino)metil)naftalen-2-ol (LIH2); (E)-1-((2-(2-(2-hidroksietoksi)etiltiyo)fenilimino)metil)naftalen-2-ol (LIIH2); (E)-2,4-di-tert-butil-6-(2-(2-(2-hidroksietoksi)etiltiyo)fenilimino)metil)fenol (LIIIH2) Schiff bazı ligantı ve son olarak 2-aminoetoksi etanol ile 3,5-ditertbutil-2- (E)-2,4-di-tert-butil-6-((2-(2-hidroksietoksi)etilimino)metil)fenol (LIVH2) Schiff bazı ligantları sentezi gerçekleştirilmiştir. Ardından metal asetat tuzları ile (Cu+2, Ni+2, Zn+2, Mn+2, Cd+2, Co+2) Schiff bazı metal kompleksleri elde edilmiştir. Elde edilen poli-OH fonksiyonel grup içeren Cu(LIH)2, Ni(LIH)2, Cu(LIIH)2 ve Ni(LIIH)2 kompleksleri 1,4-toluendiizosiyanat varlığında üretan polimerlerine dönüştürülme şartları araştırılmıştır. Cu(LIIH)2, Ni(LIIH)2, Co(LIIH)2, Cd(LIIH)2, Mn(LIIH)2, Zn(LIIH)2, Cu(LIIIH)2, Ni(LIIIH)2, Co(LIIIH)2, Cd(LIIIH)2, Cu(LIVH)2, Ni(LIVH)2, Co(LIVH)2, Mn(LIVH)2 ve Zn(LIVH)2 komplekslerinin diglisidil eter bis fenol A (DGEBFA) ile epoksi polimerlerine dönüştürülmesi şartları araştırılmıştır. Polimerleşebilen fonksiyonel gruplar içeren ligandlar, bunların metal kompleksleri ve elde edilen metallopolimerler UV, FT-IR, NMR, MASS, GPC ve termal analiz spektroskopileri ile karakterize edilmiştir. In this study, the synthesis and characterization of new type poly-functional schiff bases metal complexes, and the investigation of their polymerizability properties with different monomers were examined. Sentezlenen poli -OH fonksiyonel komplekslerin, 1,4-toluendiizosiyanat varlığında üretan polimerlerine ve glisidil eter türevleri ile epoksi polimerlerine dönüştürülmesi şartları araştırılmıştır. The Synthesized poly OH-functional complexes were investigated to determine the polymerization condition to urethane polymers in presence of 1,4–toluenediisocyanate and to epoxy polymers with diglycidyl ether, respectively. The synthesis of (E) -1-((2-(2-hydroxyethoxy)ethylimino)methyl)naphthalene-2-ol (LIH2), (E)-1-((2-(2-(2-hydroxyethoxy)ethylthio)phenylimino)methyl)naphthalene-2-ol (LIIH2), (E)-2,4-di-tert-butyl-6-((2-(2-(2-hydroxyethoxy)ethylthio)phenylimino) methyl) phenol (LIIIH2) and (E)-2,4-di-tert-butyl-6-((2-(2-hydroxyethoxy) ethylimino)methyl) phenol (LIVH2) as schiff bases ligands were performed. The hydroxyl armed complexes were prepared by utilizing the concentrated synthesis method using metal acetate salts of Cu+2, Ni+2, Zn+2, Mn+2, Cd+2 and Co+2 ions due to receiving higher yield and easy purification. Metal containing polyurethanes (PUP) were synthesized by the addition polymerization of 1,4-toluene diisocyanate (TDİ) with the prepared bis-OH functionalized Schiff base complexes [Cu(LIH)2, Ni(LIH)2, Cu(LIIH)2, Ni(LIIH)2] and chararacterized. Metal containing epoxy polymers (EPO) were prepared with the prepared bis -OH functionalized Schiff base complexes [Cu(LIIH)2, Ni(LIIH)2, Co(LIIH)2, Cd(LIIH)2, Mn(LIIH)2, Zn(LIIH)2, Cu(LIIIH)2, Ni(LIIIH)2, Co(LIIIH)2, Cd(LIIIH)2, Cu(LIVH)2, Ni(LIVH)2, Co(LIVH)2, Mn(LIVH)2, Zn(LIVH)2] in the presence of diglycydil ether bis phenol A (DGEBFA) and investigated. The prepared ligands, complexes and their PUP, EPO polymers were characterized by the combination of 1H-NMR, 13C-NMR, FT-IR, Maldi-TOF MS, GPC, UV-vis., fluorescent spectroscopy and elemental analysis data. 279

06.03.2018 tarihli ve 30352 sayılı Resmi Gazetede yayımlanan “Yükseköğretim Kanunu İle Bazı Kanun Ve Kanun Hükmünde Kararnamelerde Değişiklik Yapılması Hakkında Kanun” ile 18.06.2018 tarihli “Lisansüstü Tezlerin Elektronik Ortamda Toplanması, Düzenlenmesi ve Erişime Açılmasına İlişkin Yönerge” gereğince tam metin erişime açılmıştır. Bu tez çalışmasında farklı türde amido propil amin grubu içeren suda çözünür ftalosiyanin bileşiklerinin birinci sıra geçiş metal (Zn, Co, Ni) kompleksleri sentezlenmiş, yapı aydınlatma çalışmaları gerçekleştirilmiş, kritik misel konsantrasyonları belirlenmiş, fotofiziksel ve fotokimyasal özellikleri incelenmiştir. İlk aşama olarak, karbamat türevi propil amin grubu içeren başlangıç maddeleri (1, 2) sentezlenmiştir. Başlangıç maddelerinin 4-nitroftalonitril bileşiği ile nükleofilik aromatik sübstitüsyon reaksiyonu sonucu sonraki basamaklarda ftalosiyanin bileşiklerinin sentezinde öncül bileşik olarak kullanılacak olan ftalonitril bileşikleri (3, 4) sentezlendi. Bir diğer ftalonitril türevi olan başlangıç maddesi (5) literatür prosedürüne göre hazırlanan 4-karboksifenoksi grubunu taşıyan başlangıç maddesinin N,N-dimetil-1,3-propandiamin ile kondenzasyonundan hazırlandı. Ftalonitril bileşiklerinin yüksek kaynama noktalı bir çözücüde (n-pentanol, DMAE) metal tuzu varlığında baz katalizliğinde halka kapanması yöntemiyle amidoamin sübstitüe ftalosiyanin bileşikleri (6-14) elde edildi. Hedef moleküller olan suda çözünür ftalosiyanin bileşiklerinin (15-41) sentezi için amido amin gruplarının tersiyer aminlerinin sodyum kloroasetat, 1,3-propansulton ve hidrojen peroksit ile katılma reaksiyonları sonucu iç tuz oluşumları gerçekleştirildi. Sentezlenen bu bileşiklerin yapıları, UV-vis, FT-IR, 1H NMR, 13C NMR, LC-MS/MS, MALDI-TOF kütle spektroskopisinden elde edilen verilerin kombinasyonu ve elementel analiz ölçümleri ile aydınlatıldı. 15-41 bileşikleri için kritik misel konsantrasyonları belirlendi. Tüm hazırlanan Zn (II) ftalosiyanin türevleri (6, 15, 24, 33), (9, 18, 27, 36) ve (12, 21, 30, 39) için fotofiziksel ve fotokimyasal özellikler incelendi. Anahtar kelimeler: Suda çözünür ftalosiyaninler, sentez, çözelti özellikleri, kritik misel konsantrasyonu, floresans, singlet oksijen verimi. In this study, different type amido propyl amine group containing water soluble phthalocyanines have been synthesized as first row transition metal (Zn, Co, Ni) complexes, the characterization studies have been performed, critical micelle concentration values and photophysical and photochemical properties of synthesized complexes have been investigated. For the first step, carbamate derivative starting materials which are containing propyl amine groups (1, 2) have been synthesized. As a result of nucleophilic aromatic substitution reactions between the prepared starting materials and 4-Nitrophthalonitrile compound, the phthalonitrile derivatives (3, 4) were synthesized as the starting materials for the phthalocyanine derivatives which would be synthesized in the following steps. The other phthalonitrile derivative (5) was synthesized from the condensation reaction of the phthalonitrile compound bearing 4-Carboxyphenoxy group and synthesized according to the literature procedure with N,N-Dimethyl-1,3-propanediamine. Amidoamine substituted phthalocyanine compounds (6-14) were prepared by the cyclization reactions of phthalonitrile compounds in presence of metal salts, high boing point solvents (n-pentanol, DMAE) and steric base catalysis. For synthesis of target water soluble phthalocyanine compounds (15-41), the addition reaction of the tertiary amines of amidoamine groups with sodium chloroacetate, 1,3-Propanesultone and hydrogen peroxide were performed for zwitter ion formations. Synthesized compounds were characterized by the combination of UV-vis, FT-IR, 1H NMR, 13C NMR, LC-MS/MS, MALDI-TOF mass spectroscopic data and elemental analysis measurements. Critical micelle concentration values were measured for compounds 15-41. Photophysical and photochemical properties were investigated for all the synthesized zinc (II) phthalocyanine derivatives (6, 15, 24, 33), (9, 18, 27, 36) and (12, 21, 30, 39). Keywords: Water soluble phthalocyanines, synthesis, solution properties, critical micelle concentration, fluorescence, singlet oxygen quantum yield

Bu çalışmada Schiff bazı yapılı 2-(2-etoksietanol)-benziliden-salisilhidrazid (SAEEBSH) ligandının sentezi gerçekleştirilmiştir. Bu ligandın ilgili geçiş metali ve lantanit tuzlarıyla metanolik ve etanolik çözeltiler içinde kompleksleri sentezlenmiştir. Komplekslerin hazırlanmasında Cu(OAc)2, Cd(OAc)2.2H2O, Ni(OAc)2.4H2O, La(NO3)3.6H2O, Sm(NO3)3.6H2O ve Gd(NO3)3.6H2O tuzları kullanıldı. Daha önceden çalışma grubumuz tarafından sentezi yapılan Schiff bazı yapılı p-hidroksi benziliden-salisilhidrazid (p-HBSH)' in lantanit tuzlarıyla kompleksleri de sentezlendi. Sentezlenen hidroksil fonksiyonel grubu içeren komplekslerin metal içeren epoksi polimerleri, diglisidil eter bisfenol-A (DGEBA) ve katalizör olarak tetrabutil amonyumhidroksit (TBAH) kullanılarak hazırlandı. Kürleme şartları azot atmosfeti altında 150 °C ve 175 °C de gerçekleştirildi. Hazırlanan Schiff bazı ligantların karakterizasyonları 1H-NMR, 13C-NMR, FT-IR ve MS spektroskopi teknikleri ile gerçekleştirilmiştir. Hazırlanan Cu2+, Cd2+, Ni2+, La3+, Sm3+ ve Gd3+ komplekslerinin karakterizasyonları FT-IR, Uv-Vis, floresans spektroskopi ve MS spektroskopi metotları ile gerçekleştirilmiştir. Hazırlanan epoksi polimerlerinin karakterizasyonları FT-IR spektroskopisi ile, termal davranışları TG ve DTA analiz yöntemleri ile ve elektronik özellikleri Uv-Vis ve floresans spektoroskopisi teknikleri ile incelendi. Hazırlanan metal içeren epoksi polimerlerin termal karakterizasyonlarından, bozunma sıcaklıkları değerlendirildiğinde, bilinen epoksi polimerlerine göre termal kararlılıkların arttığı tespit edildi.Hazırlanan komplekslerin çözeltilerinde alınan floresans spektrumlarından, çözücünün dielektrik sabitine bağlı olarak belirgin bir şekilde uyarma ve emisyon pikleri arasında stokes kaymasına sahip oldukları belirlendi. Hazırlanan metal içeren epoksi polimerlerin katı faz floresanslarında ise floresans geçişlerin keskinleştiği ve ters emisyon gösterdikleri belirlendi. Bu veriler ışığında değerlendirildiğinde, hazırlanan kompleksler ve bu komplekslerin epoksi polimerleri, termal dayanımı yüksek optoelektronik malzemelerin hazırlanmasında kullanılabilirler.Uygulanan bu yöntem ise bu tür çalışmalar için bir öncü olabilir. In this study, Schiff base type ligand named as 2- (2-ethoxyethanol) benzylidene-salicyl hydrazide (SAEEBSH) were synthesized. The metal complexes were synthesized from the prepared ligand in methanol or ethanol by using related transition metal and lanthanide salts, such as Cu(OAc)2, Cd(OAc)2.2H2O, Ni(OAc)2.4H2O, La(NO3)3.6H2O, Sm(NO3)3.6H2O and Gd(NO3)3.6H2O. The complexes of p-Hydroxy benzylidene-salicyl hydrazide, which was synthesized by our group in the previous studies, were prepared with related lanthanide salts (La(NO3)3.6H2O, Sm(NO3)3.6H2O and Gd(NO3)3.6H2O).The metal containing epoxy polymers of the synthesized hydroxyl functional group containing metal complexes were prepared by using bisphenol A diglycidyl ether (DGEBA) and tetrabutylammonium hydroxide (TBAH) as the catalyst. Curing processes were carried out under Ar atmosphere in 150 °C and 175 °C.Synthesized Schiff base ligands were characterized by 1H-NMR, 13C-NMR, FT-IR and MS spectroscopy techniques. The prepared Cu2+, Cd2+, Ni2+, La3+, Sm3+ ve Gd3+ complexes were also characterized by FT-IR, Uv-Vis, fluorescence spectroscopy and MS spectroscopy methods. Synthesized epoxy polymers were characterized by FT-IR spectroscopy. TG and DTA analysis methods for thermal behaviour and Uv-Vis, fluorescence spectroscopy techniques for electronic properties were examined.It has been determined by the discussion of the decomposition temperatures determined in the thermal characterizations that the thermal stability of the prepared metal containing epoxy polymers improved when they compared with the bare species.The fluorescence spectra of the prepared complexes in different solvents had significantly stockes shifts between excitation and emission peaks depanding on the dielectric constants of the solvents. However, in the fluorescence spectra recorded in solid phase of the prepared metal containing epoxy polymers were determined that the fluorescence transitions appeared as narrowed and sharpened appconversion emissions at lower wavelengths. By the illumination of these results, it can be succeed that the prepared complexes and their metal containing polymers can be used in the manifacture of optoelectronic materials with their improved thermal stability.The applied method can also be pioneer in the field. 139