Oksijen köprülü fonksiyonel ftalosiyaninlerin sentez 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.Ftalosiyaninler 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 sübstitüentlerin eklenmesiyle yakın kızıl ötesi bölgesine hatta 700?1000 nm `deki parmak izi bölgesine kadar genişletilebilir.Bu çalışmada metalli ftalosiyaninler {M[Pc(O-BzF4]4 ( M = Cu(II), Zn(II), Co(II), Bz=Benzen} elde edilmiştir. Bu ftalosiyaninler 4-(2,3,5,6-tetraflorofenil)ftalonitril'in uygun metal tuzlarıyla [MX2] (X=Cl veya X=Ac) kinolinli ve 1,8-diazabisiklo[5,4,0] undeka-7-ene (DBU) ortamda reflux sıcaklığında siklotetramerizasyon reaksiyonuyla elde edilmişlerdir.Ftalosiyaninler uygun metotlarla saflaştırıldıktan sonra yapıları elementel analizin yanısıra IR, UV-Vis, 1H-NMR, 13C-NMR ve MS( kütle) spektrumları yardımıyla aydınlatılmıştır.Phthalocyanines (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(O-BzF4)]4 ( M=Cu(II), Zn(II), Co(II), Bz=Benzen} were obtain from cylotetramerization reaction of 4-(2,3,5,6-tetrafluorophenyl)phthalonitrile with corresponding appropriate [M(acac)2].nH2O in the presence of quinoline and 1,8-diazabicyclo[5,4,0] undec-7-ene (DBU) as a strong at reflux 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

Fonksiyonel ftalosiyaninlerin sentezi, metal sensör, optik ve elektrokimyasal 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; seçici metal sensörler, organic ince-film transistorler, boya endüstrisinde pigment v.b. olarak kullanılmaktadırlar. Çevresel faktörlere karşı kararlılık, parlaklık ve ışığa dayanıklılık gibi çok önemli özelliklere sahiptirler. 18 πelektronlu düzlemsel bir makro halka olan ftalosiyaninler dört izoindolin biriminin 1,3-konumlarından azo köprüleriyle bağlanması sonucu oluşmuş çok kararlı moleküllerdir. Bu çalışmada, periferal 3- ve 4-sübstitüe fonksiyonel iyonofor ligandlar ve onların αve β-tetra polialkol sübstitüe metalli ftalosiyaninleri, (MPc), (M= M= ZnII, CoII , MnIII X=Cl, FeIII X=Ac, CuII, PbII) sentezlenmiş ve elemental analiz, FT-IR, 1H ve 13C NMR, MS (ESI ve Maldi-TOF) ile karakterize edilmiştir. Sentezlenen komplekslerin spektroskopik özellikleri halka üzerine bağlı elektron veren sülfanil gruplarından oldukça etkilenmektedir. Komplekslerin AgI ve PdII gibi katyonları bağlama özellikleri UV-Vis spektroskopi tekniği ile incelenmiş ve H-tipi (face-toface) veya J-tipi (edge-to-edge) polinükleer ftalosiyanin komplekslerinin oluştuğu gözlenmiştir. Komplekslerin redoks özelliklerini incelemek için voltametrik ve in-situ spektroelektrokimyasal tekniklerden yararlanılmıştır. Komplekslerin elektrokimyasal yollarla elde edilen anyonik ve katyonik yapılarının renklerini incelemek için in-situ elektrokolorimetrik metodlardan yararlanılmıştır. NIR absorplama özelliği olan α-sübstitüe Mn ftalosiyanininin yarı iletken ve metal/organic yarı iletken özelliği; elektriksel iletkenlik-sıcaklık, optik absorpsiyon ve akım-voltaj karakteristik metodları ile araştırılmıştır. Elektriksel iletkenliğin sıcaklıkla artması α-sübstitüe mangan ftalosiyaninin bir organic diyot olarak kullanılabilmesini sağlayan yarı iletkenlik özelliğinin olduğunu kanıtlamıştır.Phthalocyanines are widely used as selective metal sensors, organic thin-film transistors (OTFT), paints, etc. They exhibit remarkable qualities like lightfastness, brightness and stability towards environmental influences. Pc’s consist of a planar macrocycle with an 18 п-electron system comprising four isoindole units linked together through their 1,3-positions by aza bridges, which mainly confers this known stability. In this study, peripherally 3- and 4-substituted functionalized ionophore ligands and their α- ve β-tetra polyalcohol substituted metallo phthalocyanines, (MPc), (M= M= ZnII, CoII, MnIII X=Cl, FeIII X=Ac, CuII, PbII) have been synthesized and fully characterized by elemental analysis, FT-IR, 1H and 13C NMR, MS (ESI and MaldiTOF). Spectroscopic properties of the synthesized complexes were affected strongly by the electron-donating sulfanyl units on the periphery of the phthalocyanines. Cation binding properties of the complexes such as AgI and PdII were evaluated by UV-Vis spectroscopic technique and the results show the formation of H-type (faceto-face) veya J-type (edge-to-edge) polynuclear phthalocyanine complexes. The voltammetric and in-situ spectroelectrochemical studies were performed to characterize the redox behavior of the complexes. An in-situ electrocolorimetric method was applied to investigate the colors of electro-generated anionic and cationic forms of the complexes. The semiconducting and metal/organic semiconductor properties of the newly synthesized NIR absorbing α-substituted manganase phthalocyanine have been investigated by electrical conductivity-temperature, optical absorption and currentvoltage characteristics methods. The electrical conductivity increases with the temperature, suggesting that α-substituted functional manganase phthalocyanine is an organic semiconductor as used an organic diode

Comparative Studies of Photophysicochemical Properties of Non-Peripherally Anisole/Thioanisole-Tetrasubstituted Gallium (III) Phthalocyanines Containing Oxygen/ Sulfur Bridge

This work reports on the synthesis and characterization of gallium (III) phthalocyanines (4-6) which is non-peripherally tetra-substituted with anisole or thioanisole functional groups containing oxygen or sulfur bridge. Confirmation of the phthalocyanine structures performed with a combination of elemental analysis, FTIR, 1H-NMR, UV-vis and MALDI-MS spectral data. Also, investigated and discussed the effects of non-peripherally tetra-substitution with different functional groups on the photochemical (Singlet oxygen quantum yields and photodegradation quantum yields) and photophysical properties (Fluorescence quantum yields and fluorescence behavior). In every substituent, we obtained very similar singlet oxygen quantum yields as 0.64 for (4), 0.56 for (5) and 0.65 for (6) suggesting its potential as a photosensitizer in PDT treatment

Gemini-type 1(4),8(11)-15(18),22(25)-fluoroprobe attached as macrocyclically electrovalent mononuclear and bunk-type dinuclear phthalocyanines

The new gemini designed 1(4),8(11)-15(18),22(25)-fluoroprobe attached macrocyclically electrovalent mononuclear [(Co(II) (2a), Mn(III) (3a)] and bunk-type (dimer) electrovalent dinuclear [(Co(II) (2b), Mn(III) (36)] phthalocyanines have been synthesized as a mixture from the corresponding 3,3'-(1,1'-((4-methoxy phenyl)methylene)bis(naphthalene-2,1-diyl))bis(oxy)-diphthalonitrile (1), an adjacent bis dinitrile, which is obtained from the reaction of 3-nitrophthalonitrile and 1,1'-((4-methoxyphenyl)methylene)dinaphthalen-2-ol. The extraordinary mono and dinuclear types of phthalocyanines have been separated from each other by tedious purification using their different dissolution capabilities. FTIR, H-1 NMR, C-13 NMR, UV-Vis, MALDI-TOF/MS spectral, magnetic susceptibility and elemental analysis data have been used to characterize the novel compounds. The magnetic susceptibility studies revealed that all of the mono and dinuclear complexes are paramagnetic and high-spin complexes. The spectroscopic properties of the complexes, which are organo-soluble, are affected strongly by the fluorescent units on the periphery of the phthalocyanines. The fluorescence quantum yield was affected by the molecular structures of the mono and dinuclear manganese phthalocyanines (3a and 3b), and this is discussed. It was found that the cage effect diminished the fluorescence quantum yield of the phthalocyanine structure. The redox behavior of the complexes was examined by voltammetry on Pt in DMSO/TBAP. The electrochemical measurements showed the formation of pronounced-valence oxidation and reduction species with potential shifts. (C) 2013 Elsevier Ltd. All rights reserved

Peripheral and non-peripheral-designed multifunctional phthalocyanines; synthesis, electrochemistry, spectroelectrochemistry and metal ion binding studies

A novel type of ionophore ligands, 3'-(2,3-dihydroxypropylthio)-phthalonitrile and 4'(2,3-dihydroxypropylthio)-phthalonitrile, and their alpha- and beta-tetrasubstituted metallo phthalocyanines, (MPc), (M = Zn-II, Co-II, (MnCl)-Cl-III, (FeAc)-Ac-III, Cu-II) have been prepared and fully characterized by elemental analysis, FT-IR, H-1 and C-13 NMR, and MS (ESI and Maldi-TOF). The complexes are soluble in both polar and non-polar solvents, such as MeOH and EtOH, THF, CHCl3 and CH2Cl2. The spectroscopic properties of the complexes are affected strongly by the electron-donating sulfanyl units on the periphery of the phthalocyanines. The cation binding properties of the complexes, for example using Ag-I and Pd-II, were evaluated by UV-Vis spectroscopy and the results show the formation of polynuclear phthalocyanine complexes. Functional donors on the periphery of the zinc and copper complexes coordinate to Ag-I and Pd-II to give ca. a 2:1 metal-phthalocyanine complex binding ratio for the concentration of 2.5 x 10(-5) M (Pc) and 1.0 x 10(-3) M (Metal ions). Voltammetric and in-situ spectroelectrochemical studies were performed to characterize the redox behavior of the complexes. An in-situ electrocolorimetric method was applied to investigate the colors of the electro-generated anionic and cationic forms of the complexes. (C) 2011 Elsevier Ltd. All rights reserved

Functional fluoro substituted tetrakis-metallophthalocyanines: Synthesis, spectroscopy, electrochemistry and spectroelectrochemistry

In this study, electron-withdrawing fluoro-functional ligand and its tetrakis 2,9,16,23-4-(2,3,5,6-tetrafluoro)-phenoxy-phthalocyaninatometal (II) complexes, (ZnPcOBzF(16), CuPcOBzF(16) and CoPcOBzF(16)) (Bz: benzene) which are organo-soluble have been prepared. Their structures were confirmed by elemental analysis, FT-IR, (1)H NMR, UV/vis and MS (Maldi-TOF) spectral data. Electron-withdrawing fluorine atoms on 2,3,5,6-position of benzene at the peripheral sites increases the solubility of the tetrakis-metallophthalocyanines. The cyclic voltammetry and differential pulsed voltammetry of the complexes show that while 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 MPc complexes. Spectroelectrochemical measurements confirm the assignments of the complexes. (c) 2008 Elsevier B.V. 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

Extraction of electronic parameters of organic diode fabricated with NIR absorbing functional manganase phthalocyanine organic semiconductor

The semiconducting and metal/organic semiconductor properties of the newly synthesized NIR absorbing alpha-substituted manganase phthalocyanine bearing functional 2,3-dihydroxypropylthio moieties {M[Pc(S-CH(3)CH(2)(OH)CH(2)(OH))](4)X}(M = Mn(III)) have been investigated by electrical conductivity-temperature, optical absorption and current-voltage characteristics methods. The electrical conductivity increases with the temperature, suggesting that the peripheral alpha-substituted-functional manganase phthalocyanine is an organic semiconductor. The optical band gap and trap energy values were determined and were found to be 2.98 eV and 1.95 eV, respectively. The ITO/MnPc/Al diode shows a rectifying behavior due to the formation of MnPc/Al interface with a rectification ratio of 29.4 at +/- 2 V. The series resistance R(s) and ideality factor n values were found to be 102.6 k Omega and 8.89, respectively. The interface state density for the diode was of order of 2.73 x 10(11) eV(-1) cm(-2) with the interface time constant of 1.93 x 10(-5). It is evaluated that newly synthesized alpha-substituted manganase phthalocyanine bearing functional 2,3-dihydroxypropylthio moieties is an organic semiconductor and can be used in electronic device applications as an organic diode. (C) 2011 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

Synthesis, H- or J-type aggregations, electrochemistry and in situ spectroelectrochemistry of metal ion sensing lead(II) phthalocyanines

We report, in this study, peripherally 3- and 4-substituted functionalized ionophore ligands (1-3) and their alpha- and beta-tetra polyalcohol substituted lead(II) phthalocyanines M{Pc[S-CH(C3H7)(C2FH5OH)](4)} (7, 9 and 11) and M{Pc(S-C6H12(OH)](4)) (8. 10 and 12) which are a mixture of different isomers. The complexes have been fully characterized by elemental analysis, FT-IR, H-1 NMR, C-13 NMR, MS (MALDI-TOF) and UV-Vis spectral data. These complexes induced H-type (face-to-face fashion) on-aggregate (edgeto-edge) dimers when titrated with AgNO3 or Na2PdCl4 in a THF-MeOH solution. Cyclic and square wave voltammetry studies showed that the complexes gave three one-electron ligand-based reductions and two one-electron oxidation couples having diffusion controlled mass transfer character. Assignments of these redox couples were confirmed by spectroelectrochemical measurements. The observation of split Q bands, which are characteristic spectral behavior of metal-free phthalocyanines, indicates demetallization of the complexes during the spectroelectrochemical measurement under the applied potentials. The types of the substituents on the ring of the phthalocyanines affect the demetallization process of the complexes. (C) 2010 Elsevier Ltd. All rights reserved