Sensör elektrokromik fonksiyonel ftalosiyaninler

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.Anahtar Kelimeler : Ftalosiyanin, kobalt, nikel, çinko, lantanit, elektrokimya, agregasyon, metal sensör.Ftalosiyaninler (Pc) dört pirol halkası içeren, koyu mavimsi, morumsu veya yeşilimsi, makro halkalı bileşiklerdir ve elektronik spektrumlarında yoğun absorpsiyonlar gösterirler. Molekülün merkezinde yer alan iki imino hidrojeni ftalosiyanin olarak bilinen bileşikleri oluşturmak için periyodik tablodaki hemen hemen her metal ile yer değiştirebilir. Ftalosiyaninler aynı zamanda çok sayıda fonksiyonel grup ile substitüe olabilir. Bu yüzden, ftalosiyanin sınıfı bileşikler, metalsiz ftalosiyaninler, metalli ftalosiyaninler ve onlarla alakalı türevlerden ibarettirler.Bu çalışmanın ilk kısmında, biz halka konumunda substitüe olmuş iyonofor çift katlı ftalosiyaninlerden olan lantanit bis-[(4,4',4'',4''')-tetrakis-(6-hidroksihekzilsulfonil) ftalosiyanin] ,{M[Pc(S-C6H13OH)4]2} (M=PrIII, YbIII, and LuIII)'in hazırlanmasını, fiziksel karekterizasyonunu ve elektrokimyasını sunmaktayız. Çift katlı ftalosiyaninlerdeki bütün benzenlere metal iyon bağı ve yüzey bağı gibi potansiyel kullanıma sahip olan hidroksihekzilsulfonil parçacıkları ilave edilerek fonksiyonel yapılmıştır. Çift katlı ftalosiyaninler susuz metal tuzlarıyla {Ln(acac)3} ve Ag+ ve Pd+2 nin varlığında optikal değişim gösteren 4'-(6-hidroksihekzilsülfonil)-1,2-disiyanobenzenden sentezlenmiştir. Yeni sentezlenmiş lantanit çift katlı ftalosiyaninler metanolde (MeOH), etanolde (EtOH) , tetrahidrofuran (THF), dimetilformamitde (DMF), dimetisulfoksitte (DMSO), kloronaftalende, kinolinde çözünürken i-Pr-OH da ve asetonitrilde daha az çözünür.Bu çalışmanın son aşamasında biz yeni tip reseptör ligandın ve onun tetrasübstitüe, halka konumunda sülfür ve oksijen donör atomları içeren ftalosiyaninlerin 2,9,16,23-tetrakis(6-hidroksihekzilsülfonil) ftalosiyanin, M[Pc(SC6H13O(M=Zn(ll), Cu(ll), Co(ll), sentezi gerçekleştirilmiş ve bu bileşikler elementel analiz, FTIR, 1H ve 13C NMR, MS (ESI ve MALDİ-TOF) ve UV-Vis spektral verileri yardımıyla karekterize edilmiştir. Yeni sentezlenmiş fonksiyonel ftalosiyaninler MeOH, EtOH, THF, DMF, CNP (?-kloronaftalin), DMSO ve kinolin de çözünürken, i-PrOH ve CH3CN gibi solventlerde daha az çözünür.Keywords: Phthalocyanine, cobalt, nickel, zinc, lanthanides, electrochemistry, aggregation, metal sensör.Phthalocyanines (Pc) are macrocyclic compounds containig four pyrole units having dark blue, purple or green colours and exhibiting intense absorptions in their electronic spectra. The two imino-hydrogen atoms in the centre of molecule can be replaced by almost any metal in the periodic table to form the compounds known as phthalocyanine. They can also be substitued by numerous functinonal groups. Therefore, the phthalocyanine class of compounds consist of metal-free phthalocyanines metallophthalocyanines and related derivatives.In the first part of this study, we report the preparation, physical characterization and electrochemistry of peripherally substitued ionophore double-decker lanthanide phthalocyanines, lanthanide bis-[(4,4?,4??,4??)-tetrakis-(6-hydroxyhexylsulfanly) phthalocyanines] ,{M[Pc(S-C6H13OH)4]2} (M=PrIII, YbIII, and LuIII). All benzenes on the double-decker phthalocyanines are functional with hydroxyhexylsulfanyl moieties for potential use as metal ion binding and surface anchors. The double-decker phthalocyanines synthesized from the anhydrous metal salts {Ln(acac)3} and the corresponding 4?-(6-hydroxhexylsulfanyl)-1,2-dicyanobenzene exhibit ion-specific optical change in the presence of Ag+ and Pd2+. Newly synthesised lanthanide double-decker phthalocyanines are soluble in methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylsulfoxide (DMSO), chloronapthalene, qunoline and less soluble in i-Pr-OH and acetonitrile.In the last part of this study, we tried to make synthesis of novel type of receptor ligand and its tetrasubstitüed phthalocyanines, 2,9,16,23-tetrakis(6-hydroxyhexylsulfanly) phthalocyanine,M[Pc(S-C6H13OH)4](M=Zn (ll),Cu(ll),Co(ll), bearing sulfur and oxgen donor atoms on the periphery together with The new synthesized compounds have been characterized by elemental analysis, FTIR, 1H and 13C NMR , MS ( ESI and MALDİ-TOF ) and UV-Vis spectral data. These compounds were soluble in MeOH, EtOH, THF, DMF, CNP ( ?-chloronapthalene ), DMSO and quinoline, and less soluble in i-PrOH and CH3CN

Synthesis, characterization and electrochemistry of novel differently octasubstituted phthalocyanines

We describe the complete synthesis of differently substituted multifunctional metallo phthalocyanines (MPcs) (M = Ni, Zn, Cc) bearing four 2'-aminophenylsulfanyl or 2-aminophenoxy moieties and four chloro atoms on peripheral positions. The synthesis started from the corresponding anhydrous metal salts and differently substituted [4-(2'-aminophenylsulfanyl)-5-chlorobenzene-1,2dicarbonitrile] (2a) and [4-(2-aminophenoxy)-5-chlorobenzene-1,2-di-carbo nitrile] (2b), and the products were separated by HPLC. These multifunctional amino substituents serve as strong binding sites for further reactions after phthalocyanine formation, such as Schiff-bases, and provide solubility of the phthalocyanines in organic solvents (THF, CHCl3 and CH2Cl2). The newly synthesized compounds have been characterized by elemental analysis, FTIR, H-1 NMR, MS (EI and FAB), UV-Vis and atomic absorption spectroscopy. Electrochemical studies reveal that CoPc (6a) has two metal and four ligand-based redox processes while NiPc (4a) and ZnPc (5b) show three ligand-based reduction processes. (C) 2002 Elsevier Science Ltd. All rights reserved

Metal-ion sensing and aggregation studies on reactive phthalocyanines bearing soft-metal receptor moieties; synthesis, spectroscopy and electrochemistry

Tetrasubstituted metal-free {2H[Pc(S(CH(2))(6)OCOC(4)H(3)S)(4)]} and copperphthalocyanine {Cu[Pc(S(CH(2))(6)OCOC(4)H(3)S)(4)]}, bearing thiophene-2-carboxylate-hexylthio moieties, have been prepared as isomeric mixtures via cyclo-tetramerization. Both new compounds have been characterized by elemental analysis, FTIR, (1)H and (13)C NMR, MS (Maldi-TOF) and UV-Vis spectral data, The cation binding abilities of the functional phthalocyanines with Ag(I), Pd(II), Hg(II), Pb(II) and Cd(II) are evaluated by a monomer-oligomer formation technique with U-V-Vis spectroscopy. Spectroscopic properties of the complexes were affected strongly by the electron-donating sulfanyl units on the periphery. Cyclic voltammetry and differential pulse voltammetry studies show that both compounds give up to three ligand based reduction processes and one ligand-based oxidation process having diffusion-controlled one electron transfer properties. (C) 2007 Elsevier Ltd. All rights reserved

Voltammetry and spectroelectrochemical behavior of a novel octapropylporphyrazinato Lead(II) complex

The synthesis, characterization, and voltammetric and spectroelectrochemical investigation of [2,3,7,8,12,13,17,18-octapropyl porphyrazinato] lead(II) are reported. The characterization of newly synthesized lead porphyrazine was made by elemental analysis, H-1 NMR, FT-IR, UV-vis, and MALDI-TOF. The solution redox properties and spectroelectrochemical investigation of the novel lead(II) porphyrazine were studied using various electrochemical techniques in DCM on a platinum electrode. Cyclic voltammetry and differential pulse voltammetry studies show that the complex gives two one-electron ligand-based reductions and a oneelectron oxidation wave having diffusion-controlled mass transfer character. Assignments of the redox couples were confirmed by spectroelectrochemical measurements. Spectroelectrochemical studies reveal that the complex is demetalized during the controlled potential coulometry measurement after the first reduction couple of the complex

Electrical transport and optical properties of an organic semiconductor based on phthalocyanine

Electrical conductivity, thermoelectric power and refractive index disperson properties of the Co(II) complex of tetrasubstituted thiophene-attached phthalocyanine have been investigated for the first time. The electrical conductivity of the sample increases with increase in temperature. Electrical conductivity and thermoelectric power results suggest that the 2, 9, 16, 23-tetrakis-6-(-thiophene-2carboxylate)-hexylthio-phthlocyaninato cobalt (II) complex {M[Pc(S(CH2)(6)OCOC4H3S)(4)]; {M = Co (II)} (CoPc) sample is a p-type organic semiconductor. The electrical conductivity mechanism changes from thermally activated conductivity to the conductivity by hopping in the localized states. The refractive index at infinite wavelength and optical band gap of the CoPc sample were found to be 3.43 and 3.65 eV, respectively. (c) 2007 Elsevier B.V. All rights reserved

Polytopic cation receptor functional phthalocyanines: Synthesis, characterization, electrochemistry and metal ion binding

Our efforts toward the development of the synthesis of a novel type of receptor ligand and its tetrasubstituted phthalocyanines, 2,9,16,23-tetrakis(6-hydroxyhexylsulfanyl) phthalocyanine, M[Pc(S-C6H13OH)(4)] (M = Zn(II), Cu(II), Co(II)), bearing sulfur and oxygen donor atoms on the periphery together with hexyl moieties, have been carried out together with spectroscopic and electrochemical characterization. The newly synthesized functional phthalocyanines were soluble in MeOH, EtOH, THF, DMF, CNP (alpha-chloronapthalene), DMSO and quinoline, and less soluble in i-PrOH and CH3CN. Cation binding abilities of the functional phthalocyanines with Ag+, Pd2+, Hg2+ and Cd2+, resulting in the formation of polynuclear phthalocyanine complexes, were evaluated by UV-Vis spectroscopic techniques. The spectroscopic properties of the complexes were affected strongly by the electron-donating sulfanyl units on the periphery. The cyclic voltammetry of the complexes were examined on a platinum electrode in DMSO. The new synthesized compounds have been characterized by elemental analysis, FTIR, H-1 and C-13 NMR, MS (ESI and MALDI-TOF) and UV-Vis spectral data. (c) 2006 Elsevier Ltd. All rights reserved

Synthesis and photophysical properties of metallophthalocyanines substituted with a benzofuran based fluoroprobe

The synthesis, characterization and photophysical properties of the tetra- {6-(-benzofuran-2-carboxylate)-hexylthio} substituted copper(II), cobalt(II), manganese(III) and zinc (II) phthalocyanines, {M[Pc(beta-S(CH2)(6)OCOBz-Furan)(4)], which were derived from 6-(3,4-dicyanophenylthio)-hexyl-2-benzofuranate (BzF) (1-4) are reported for the first time. The new compounds have been synthesized and fully characterized by elemental analysis, FTIR. UV-vis, H-1- and C-13 NMR, MS (Maldi-TOF). In this work, we also report the effects of peripherally bound BzF substituent on the photophysical properties of metallo phthalocyanine derivatives. The effects of changing the central metal ions on quantum yield are discussed. It was found that the substitution of BzF groups on the framework of phthalocyanines diminished the fluorescence quantum yield of these complexes depending on paramagnetic behavior of central metal atoms. In addition, central metal atoms like Co and Cu also caused to decrease in quantum yield of phthalocyanine backbone. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved

Functional alcohol-soluble double-decker phthalocyanines: synthesis, characterization, electrochemistry and peripheral metal ion binding

In this study we report the preparation, physical characterization and electrochemistry of peripherally functionalized substituted ionophore double-decker lanthanide phthalocyanines, lanthanide bis-[(4,4',4",4"')-tetrakis-(6-hydroxyhexylthio)phthalocyaninates], {M[Pc(S-C6H13OH)(4)](2)} (M = Pr-III, Yb-III, and Lu-III). All benzenes on the double-decker phthalocyanines are functionalized with hydroxyhexylsulfanyl moieties for potential use as metal ion binding and surface anchors. The double-decker phthalocyanines synthesized from the anhydrous metal salts {Ln(acac)(3)} and the corresponding 4-(6-hydroxyhexylthio)-1,2-dicyanobenzene exhibit ion-specific optical changes in the presence of Ag+ and Pd2+. Thio donors of the complexes coordinate to Ag+ and Pd2+ to give 4:1 metal-phthalocyanine complexes. Newly synthesized lanthanide double-decker phthalocyanines are soluble in methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylsulfoxide (DMSO), chloronapthalene, quinoline and less soluble in i-PrOH and acetonitrile. Electrochemical studies reveal that all lanthanide-base complexes undergo ligand-based redox processes. The smaller HOMO-LUMO gaps of the complexes indicate the existence of strong pi-orbital interactions between the rings of the sandwich. The newly synthesized compounds have been characterized by elemental analysis, FTIR, H-1 and C-13 NMR, MS (ESI and MALDI-TOF), UV-vis and EPR spectral data. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines

Selective heavy metal receptor functional phthalocyanines bearing thiophenes: Synthesis, characterization, spectroscopy and electrochemistry

Soft metal ion receptor 2,9,16,23-tetrakis-6-(-thiophene-2-carboxylate)-hexylthio-phthlocyaninato zinc(II) and cobalt(II) complexes derived from 6-(3,4-dicyanophenylthio) hexyl thiophene-2-carboxyl ate have been prepared as an isomeric mixture via cyclotetramerization reactions. The complexes have been fully characterized by elemental analysis, FTIR, H-1 and C-13 NMR, MS (ESI and MALDI-TOF) and by UV-vis spectral data. Soft metal ion binding ability of the complexes with Ag-I, Pd-II, Hg-II and Cd-II has been evaluated by UV-vis spectroscopic titration technique. Cyclic and differential pulse voltammetries show that while Zn(II)Pc gives up to two ligand-based reduction and one ligand-based oxidation processes having diffusion-controlled reversible electron transfer properties, Co(II)Pc represents one ligand-based and one metal-based oxidation and one metal-based and one ligand-based reduction processes having diffusion-controlled reversible electron transfer characters. Assignments of the redox couples of Co(II)Pc are confirmed by spectroelectrochemical measurements. (C) 2007 Elsevier Ltd. All rights reserved

Synthesis, spectroscopy and electrochemical properties of highly soluble fluoro containing phthalocyanines

2(3),9(10),16(17),23(24)-Tetrakis-4'-[3,5-bis-(trifluoromethyl)-phenoxy]-phthalocyanines, {M[Pc-beta(OBz-(CF3)(2))(4)]}, (M = Zn(II), Cu(II), Co(II) and Ni(II)) were synthesized and characterized by elemental analysis, FTIR, H-1 NMR, UV-Vis and MS (Maldi-TOF) spectral data. It is shown that the 4-(3,5-bis(trifluoromethyl)-phenoxy) moieties on the periphery affect the solubility, spectroscopic data and electrochemistry of the tetrakis metallophthalocyanines. The cyclic voltammetry and differential pulsed voltammetry of the complexes give well-defined redox couples in harmony with common metallophthalocyanine complexes. Electrochemical studies show that the complexes exhibit stable monoanionic M{Pc-beta-[(OBz-(CF3)(2))(4)]}(1-) dianionic M{Pc-beta-[(OBz-(CF3)(2))(4)]}(2-) and monocationic M{Pc-beta-OBz-(CF3)(2))(4)]}(1+) species during the reduction and oxidation processes. When compared with the unsubstituted analogues, the redox potentials of the complexes shifted to more positive potentials due to the electron-withdrawing fluorine groups. (C) 2008 Elsevier Ltd. All rights reserved