Seçici metal duyarlı ftalosiyaninlerin hazırlanması ve elektriksel özelliklerinin incelenmesi

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.Ftalosiyaninler genellikle mavi, yeşil renkli, yüksek ısıya, ışığa dayanıklı kimyasal olarak kararlı fakat çözünürlüğü çok az olan bileşiklerdir. Bu nedenle ftalosiyanin sentezinde çözünürlüğü yüksek ürünler elde etmek önem kazanmaktadır. Bu çalışmanın ilk aşamasında biz yeni tip reseptör ligandın ve onun hekzasübstitüe, halka konumunda sülfür donör atomları içeren ftalosiyaninlerin 2,3,7,8,12,13,17,18– oktakis{1–hidroksihekzan–3–yiltiyo)–ftalosiyaninato[M=Zn(II), Cu(II), Co(II), Pb(II), Mn(III)], sentezi gerçekleştirilmiştir. Yeni sentezlenmiş fonksiyonel ftalosiyaninler MeOH, EtOH, CHCl3, THF, DMF, DMSO ve kinolin de çok çözünürken, i-PrOH ve CH3CN gibi solventlerde daha az çözünmektedir. Bu çalışmanın ikinci kısmında, biz halka konumunda substitüe olmuş çift katlı ftalosiyaninlerden olan Bis-({[4, 5, 4′, 5′, 4″, 5″, 4’’’, 5’’’] - oktakis{1– hidroksihekzan–3–yiltiyo)–ftalosiyaninato}lantanit], (M=LuIII, YbIII, and LaIII)’in sentezi gerçekleştirilmiştir. 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 çözünmektedr. Bu çalışmada, sentezleri gerçekleştirilen bileşiklerin yapıları FT-IR, elementel analiz, kütle spektrometresi, 1H, 13C-NMR karakterize edilmiş ayrıca elektriksel ve elektrokimyasal özellikleri incelenmiştir.Generally, phthalocyanines are compounds which are blue, green colour, thermally and chemically stabile but less soluble. For that reason, the synthesis of high soluble phthalocyanines are extremely important. In the first part of this study, we tried to make synthesis of novel type of receptor ligand and its hekzasubstitued phthalocyanines, 2,3,7,8,12,13,17,18–octakis{1– hydroxyhexan–3–ylthio)–phthalocyaninato[M=Zn(II), Cu(II), Co(II), Pb(II), Mn(III)], bearing sulfur donor atoms on the periphery together with. These compounds were soluble in MeOH, EtOH, THF, DMF, CHCl3, DMSO and quinoline, and less soluble in i-PrOH and CH3CN. In the second part of this study, we report the preparation of substitued doubledecker lanthanide phthalocyanines, Bis-({[4, 5, 4′, 5′, 4″, 5″, 4’’’, 5’’’] - octakis{1– hydroxyhexan–3–ylthio)–phthalocyaninato}lantanit], (M=LuIII, YbIII, and LaIII). 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. The structure of these compounds were characterised by FT-IR, MALDI-TOF spectrometry, 1H, 13C-NMR spectra, elemental analysis and also ıts electrical and electrochemical properties were investigated

Flor fonksiyonel grup içeren yeni tip ftalosiyaninlerin sentezi ve karekterizasyonu

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:Ftalosiyaninler, Flor, Çinko, Metalsiz, Bakır, KobaltFtalosiyaninler 1,3 pozisyonunda aza köprüleriyle birbirine bağlı dört izoindol ünitesinden oluşan 18 ?-elektron sistemine sahip aromatik makrosiklik yapılardır. Bu makrosiklikler üzerindeki 2-boyutlu -elektron delokalizasyonu nadir fiziki özelliklerinin büyük miktarlarda artışına sebep olur. Bu yüzden, Ftalosiyaninler olağanüstü optiksel ve elektriksel davranışlar gösteren kimyasal ve termal olarak dayanıklı bileşiklerdir ve ma1zeme bilimi alanında çok geniş bir uygulama alanı bulurlar. Ftalosiyaninler, 70'ten fazla metalik ve ametalik katyon ile kompleks oluşturabilirler. Çok çeşitli substitüentlerin makrosiklik yapının periferal konumlarına eklenmesi bu sistemin elektronik yapısını değiştirebilir, bu grupların hacimli veya uzun zincirli hidrofobik türevler olmaları ftalosiyaninlerin- Çoğu organik çözücüler içerisindeki çözünürlüklerinin artmasına sebep olur. Görünür bölgede ftalosiyaninler mavi, siyan ve yeşil renklerle sınırlı olmalarına rağmen absorbsiyonları, uygun kimyasal substitüentlerin eklenmesiyle yakın infrared bölgesine hatta 700?1000 nm `deki parmak izi bölgesine kadar genişletilebilir.Bu çalışmada metalli ftalosiyaninler {M[Pc(S-BzF4]4 ( M = Cu(II), Zn(II), Co(II), Metalsiz Bz=Benzen} elde edilmiştir. Bu ftalosiyaninler 4 - ( 2, 3, 5, 6 -tetrafluorophenylthio)phthalonitrile'in uygun metal tuzlarıyla [MX2] (X=Cl veya X=Ac) kinolinli ve 1,8-diazabisiklo[5,4,0] undeka-7-ene (DBU) ortamda riflaks sıcaklığında siklotetramerizasyon reaksiyonuyla elde edilmişlerdir.Ftalosiyaninler uygun metotlarla saflaştırıldıktan sonra yapıları elementel analizi yanısıra IR, UV-Vis, 1H-NMR, 13C-NMR ve MS( kütle) spektrumları yardımıyla aydınlatılmıştır.Keywords: Phthalocyanines, Flour, Zinc, Free, Cobalt, CupperPhthalocyanines (Pcs) are 18 ?-electron aromatic macrocycles comprising four isoindole units linked together through their 1,3-positions by aza bridges. The particular two-dimensional -electron delocalization over these macrocycles gives rise to a great number of unique physical properties. Thus, Phthalocyanines are chemically and thermally stable compounds that exhibit exceptional optical and electrical behavior. For these reasons, they find wide application in the area of materials science. Phthalocyanines are capable of incorporating more than 70 different metallic and nonmetallic cations in their ring cavity. It is also possible to attach a wide variety of substituents at the periphery of the macrocycle, which can alter the electronic structure of the system, and, when these groups are bulky or long chain hydrophobic moieties, can serve to increase the solubility?s of Phthalocyanines in common organic solvents. In the visible region, phthalocyanines are limited to blue, cyan and green colors. However, their absorption may be extended into the near infrared and by suitable chemical engineering it is possible to fingerprint the 700 - 1000 nm region.In the present work metallophtalocyanines {M[Pc(S-BzF4)]4 ( M=Cu(II), Zn(II), Co(II), Free Bz=Benzen} were obtain from cylotetramerization reaction of 4-(2,3,5,6-tetrafluorophenylthio)phthalonitrile with corresponding appropriate [M(acac)2].nH2O in the presence of qunolin and 1,8-diazabicyclo[5,4,0] undec-7-ene (DBU) as a strong at reflax temperature.All of the phthalocyanines were purified by chromatography. The elemental analysis, IR, UV-Vis, 1H-NMR, 13C-NMR and MS (Mass) spectra confirm the proposed structures of the compound

Metal ion sensing functional mono and double-decker lanthanide phthalocyanines: Synthesis, characterization and electrical properties

We report, in this study, the preparation, physical characterization metal ion sensing properties of peripherally functionalized ionophore ligand, 4,5-bis(6-hydroxyhexylthio)-1,2-dicyanobenzene (1) and its mono 2,3,7,8,12,13,17,18-octakis(6-hydroxyhexylthio)phthalocyaninatometal (II) {M=Zn(II) (2), Cu(II) (3)} and double-decker lanthanide bis-phthalocyanines, {([4,5,4',5' 4 '',5 '',4'''5''']-tetrakis-(6-hydroxyhexylthio)phthalocyanitlatolanthanium(III)}){M[Pc(S-C(6)H(13)OH)(4)](2)} {M=Eu(III) (4), Yb(III) (5), and Lu(III) (6)}. All benzenes on phthalocyanines are functionalized with hydroxyhexylsulfanyl moieties for potential use as soft metal ion binding, such as Ag(+) and Pd(2+). The temperature dependence of the do and ac conduction properties of 4, 5 and 6 thin films have been investigated in the frequency range of 40-10(5) Hz and temperature range 290-436 K. The do results showed an activated conductivity dependence on temperature for all films. Obtained data reveal that ac conductivity obeys the relation sigma(ac)(omega)=A omega(s) and exponent is found to decrease by increasing temperature. The data obtained results were compared with the prediction of the Quantum Mechanical Tunelling (QMT) and Correlated Barrier Hopping (CBH) models. The analysis showed that the CBH model is the dominant conduction mechanism for the electron transport in the films. The new synthesized compounds have been characterized by elemental analysis, FTIR, (1)H and (13)C NMR, MS, UV-vis and EPR spectral data. (C) 2009 Elsevier B.V. All rights reserved

Tetrakis-Phthalocyanines Bearing Electron-Withdrawing Fluoro Functionality: Synthesis, Spectroscopy, and Electrochemistry

In this study, 2,9,16,23-tetrakis-4'(2,3,5,6-tetrafluoro)-phenoxy-phthalocyaninato-metalfree and metal(H) complexes, (H(2)PcBzF(16), ZnPcOBzF(16), CuPcOBzF(16), and CoPcOBzF(16)) (Bz: Benzene) (2H, Zn, Cu, and Co), have been prepared directly from the corresponding 4'-(2,3,5,6-fluorophenylthio)-phthalonitrile compounds in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in high boiling quinoline solvent. Tetrafluoro atoms on 2,3,5,6-position of benzene at the peripheral sites of phthalocyanines (Pcs) give rise interesting solubility to tetrakismetallophthalocyanines. Although all complexes were soluble in DCM, CHCl3, THF, DMF, and DMSO with increasing order, complexes synthesized, particularly H(2)PcBzF(16), CuPcOBzF(16), have very limited solubility in DMF and DMSO. The complexes have been characterized by elemental analysis, FTIR, H-1 NMR, UV-vis, and MALDI-TOF mass spectral data. The cyclic voltammetry and differential pulsed voltammetry of the complexes show that while H(2)PcBzF(16), CuPcOBzF(16), and ZnPcOBzF(16) give ligand-based reduction and oxidation processes, CoPcOBzF(16) gives both ligand and metal-based redox processes, in harmony with the common metallophthalocyanine complexes. Redox processes due to both aggregated and disaggregated species were simultaneously observed during the first reduction process. The nature of the metal-based redox processes was confirmed using spectroelectrochemical measurements. (C) 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:262-271, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.2054

Optical dispersion parameters based on single-oscillator model and optical absorption of nanocrystalline metal phthalocyanine films: A comparison study

Nanocrystalline thin films of {Co(II), Cu(II), Mn(III), Pb(II) and Zn(II)) phthalocyanine complexes were deposited by spin coating sol gel technique. The surface morphologies of the films are found to be dependable on the type of the metal complex. The absorption spectra of the films show two well defined absorption bands of phthalocyanine molecule; namely Soret (B-band) and Q-bands. The Q-band absorption of the phthalocyanine complexes shifts to longer wavelength with the central metal change. The analysis of the spectral behavior of the absorption coefficient (alpha) in the absorption region revealed two expected indirect transitions. The refractive index (n) and the absorption index (k) were calculated using the measured data of the transmittance T(lambda) and reflectance R(lambda) coefficients. The dispersion parameters such as dispersion energy (E-d), oscillator energy (E-o), high frequency dielectric constant (epsilon(infinity)'), and lattice dielectric constant (epsilon(L)) were determined using the single oscillator model. The main reason for the change in dispersion parameters of the phthalocyanine complexes may be attributed to the intensity of the metal coordination bonds that are dependent on the bound metal atoms due to their electronegativity change. The founded results of the nano-crystalline metal phthalocyanine thin films can be useful for optoelectronic applications. Discussion of the obtained results and their comparisons with the available published literature were also considered. (c) 2013 Elsevier Ltd. All rights reserved

Ag(I) and Pd(II) sensing, H- or J-aggregation and redox properties of metal-free, manganase(III) and gallium(III) phthalocyanines

H- or J-aggregation, Ag(I) and Pd(II) sensing and redox behaviours of novel a-substituted free-base (2), manganase(III) (3) and gallium(III) (4) phthalocyanines bearing 1-hydroxy hexane-3-ylthio moieties have been studied. H-1 NMR, FTIR, MALDI-TOF/MS, UV-Vis spectral and elemental data were used to characterize these new compounds. Upon addition of Ag(I), Pd(II), Mn(II), Co(II), Zn(II), Na(I), K(I) and Mg(II) ions to the solution of 2,3 and 4 in THF, only Ag(I), Pd(II) among them led to significant changes in their electronic absorption spectra, in particular, the Q- and the B-bands on the basis of donor acceptor interactions on the periphery in 2 and 3. Thus, in situ UV-Vis spectrotitration measurements suggested that 2 and 3 displayed high and reversible sensitivity towards Ag(I) and Pd(11) ions, as a result of the soft-metal responsive H- and J-aggregation behaviours. On the other hand, Ga(III)PcCl (4) with chlorine atoms at the axial positions and with large metal radii in the core did not show remarkable response to any ions. The binding ratio of 2 and 3 for Ag(I) was calculated as 1:1 and 1:2. AFM (Atomic Force Microscopy) was also used as complementary technique to investigate the morphology and to image the interfacial aggregates of 3. Compounds 2 and 4 showed ligand-based redox couples while 3 displayed well-defined ligand- and metal-based electrochromic processes. The existence of oxygen in solution was found to affect the redox behaviour of manganase phthalocyanine complex significantly, due to the formation of mu-oxo manganase phthalocyanine species. (C) 2013 Elsevier Ltd. All rights reserved

Acridine-derivated receptor for selective mercury binding based on chelation-enhanced fluorescence effect

In this study, 9-acrylamidoacridine (VAc) was synthesized by the reaction of 9-aminoacrydine (Ac) and acryloyl chloride and characterized by elemental analysis, FUR, NMR spectroscopy. The photophysical properties of VAc were elucidated by UV-vis and fluorescence measurements and quantum yield in ethanol was calculated (Phi(F) = 0.15). We have found that VAc exhibited selective fluorescence enhancement upon titration with Hg2+ ion in buffered aqueous-ethanol solution (1:1, v/v) at pH 6.0, whereas the fluorescence emission of VAc was quenched upon addition of other divalent transition-metal ions. Further, pH-dependent change in fluorescent property of VAc was observed and pKa value was determined using data of integrated emission intensity versus pH. This unique property allows the evaluation of both pH of the solution and the selective recognition of Hg2+ ion among the other metal ions. In addition, the stoichiometry of complex between VAc and Hg2+ ion was elucidated as VAc-Hg-2(2+) (1:2) applying by spectrofluorometric titration, and association constant was calculated as to be K = 1.42 x 10(8) M-2. (C) 2012 Elsevier B.V. All rights reserved

Highly selective thioalcohol modified phthalocyanine sensors for Ag(I) and Pd(II) based on target induced J- and H-type aggregations: synthesis, electrochemistry and peripheral metal ion binding studies

We have described highly selective 1(4), 8(11), 15(18), 22(25)-(1-hydroxyhexan-3-ylthio)-phthalocyanine sensors, M{Pc[alpha-SCH(C3H7)(C2H5OH)](4)} (MPc(alpha-HHT)(4), where M = Zn(II) (2), Cu(II) (3) or Co(II) (4) and HHT: -SCH(C3H7)(C2H5OH)). The formation of S-M-S {S = sulfur; M = Ag(I) or Pd(II)} bonds on the periphery in the case of Ag(I) and Pd(II) metal ions induces H-or J-aggregation, respectively, which results in significant changes in the absorption of the B-and, in particular, the Q-band. The binding ratios of Ag(I) to the periphery of 2 and 3 were found to be ca. 2 : 1 and 3 : 2, respectively. On the other hand, the binding ratios of Pd(II) to the periphery of the same compounds were found to be 3 : 1 and 4 : 1. The fluorescence of 2 exhibited distinct changes in response to treatment with Ag(I) and Pd(II) ions in solution. The fluorescence spectra emission intensity of 2 was quenched upon titration with Ag(I) and Pd(II) and a new emission maximum was observed upon titration with Pd(II). FTIR, H-1-NMR, C-13-NMR, UV-vis, MALDI-TOF MS and elemental analysis data were used to characterize the novel compounds. Transmission electron microscopy (TEM) and field-emission scanning electron microscopy (FE-SEM) were also used as complementary techniques to investigate the morphology and to image the interfacial aggregates of 2. The redox behaviours of the complexes were examined by voltammetry and in situ spectroelectrochemistry on Pt in a nonaqueous medium

H-type aggregation of functional metal ion sensing phthalocyanines: Synthesis, characterization and electrochemistry

We report, in this study, the preparation and physical characterization of the peripherally functionalized ionophore ligand, 4,5-bis(6-hydroxyhexan-3ylthio)-1,2-dicyanobenzene (1) and its branched thioalcohol-substituted phthalocyanines, 2,3,7,8,12,13,17,18-octakis{6-hydroxyhexan-3-ylthio)-metal (II) or (III) phthalocyanines (M(Pc[SCH(C(3)H(7))(C(2)H(5)OH)](8)) {M = Pb(II) (2), Zn(II) (3), Cu(II) (4), Co(II) (5) and Mn(III), X = Cl(-) (6)) which can selectively bind soft-metal ions such as silver (I) and palladium (II). It was observed by means of UV-Vis absorption spectrophotometry that the aggregates formed lead to a low solubility of the phthalocyanines in protic solvents, such as low molecular alcohols. However, the addition of AgNO(3) and Na(2)PdCl(4) into a THF-MeOH solution of {M{Pc[SCH(C(3)H(7))(C(2)H(5)OH)](8)X) (M = Pb(II) (2), Zn(II) (3), Cu(II) (4), Co(II) (5) and Mn(III), X = Cl- (6)) induced optical changes, which indicated the formation of twisted H-type dimers (blue shift, face-to-face fashion) of (M(Pc[SCH(C3H7)(C2H5OH)18) complexes, bound by four PdCl(2) and AgNO(3) units in THF solution. Elemental analysis data, matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF/MS), FT-IR, (1)H, (13)C NMR, and UV-Vis spectral data were used as complementary techniques. Voltammetry and in situ spectroelectrochemistry of the complexes were performed on Pt in DMSO/TBAP. The first reduction and oxidation processes of 5 were found to be split due to the presence of facile equilibria between the species coordinated differently at axial positions. The Mn(III)Pc(-2)X(-) complex (6) displayed well-defined colour changes during its reduction processes. The redox behaviour of the Mn(III)Pc( -2)X- complex was observed to be affected significantly by the existence of oxygen in solution due to the formation of mu-oxo MnPc species, Mn(III)Pc-O-PcMn(III). This effect was clarified well by in situ spectroelectrochemical measurements. (C) 2010 Elsevier Ltd. All rights reserved

Selective chemosensor phthalocyanines for Pd2+ ions; synthesis, characterization, quantum chemical calculation, photochemical and photophysical properties

In this study, ligand (1) was prepared by a nucleophilic displacement reaction of (4-bromophenyl) methanethiol with 4-nitrophthalonitrile according to literature and its novel type peripheral substituted tetra phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4)] were prepared. The phthalocyanines obtained from compound (1) were characterized by FT-IR, H-1 NMR, UV-Vis spectral data, elemental analysis, and MALDI-TOF. The novel phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4)] were highly soluble in common organic solvents such as CHCl3, THF, CH2Cl2, DMSO and DMF. The effect of Pd2+ ions on the fluorescence emission and UV-Vis spectra were performed with addition of increasing amounts of Pd2+ ions. This functional phthalocyanines exhibited H-type aggregation versus Pd2+ ions due to special chemical structures, which can be used as a selective chemosensor for Pd2+ ions. Also, the molecular reactivity of the ligand (1) and related metallo phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4)] were investigated and compared with the analysis of frontier molecular orbitals. In addition, photochemical and photo physical properties of these new phthalocyanines (fluorescence quantum yields, fluorescence behavior, singlet oxygen and photodegradation quantum yields) were studied in DMSO. (C) 2018 Elsevier B.V. All rights reserved