Farklı fonksiyonel sübstitüenli fitalosiyaninlerin sentez ve özelliklerinin incelenmesi

Abstract

ÖZET Anahtar Kelimeler: Ftalosiyanin, Ftalonitril Türevleri, Nikel, Çinko, Cobalt Sitokrom, Hem ya da Klorofil gibi makro halkaları taşıyan doğada bulunan önemli bileşiklerle benzerlikleri bulunan, pigment ve boyar madde olarak ticari kullanımları yarımda yüksek teknolojik uygulamalar olan ftalosiyaninler ileri malzemeler olarak yoğun bir şekilde araştırılmaktadır. Kullanım alanları gelişen teknolojiye paralel olarak geniş alana yayılmasına neden olmuştur. Bu malzemelerin boya, elektriksel malzeme olarak kullanımlarının yanında optik, yakıt pilleri, sensörler, fotodinamik kanser terapi, katalizör olarak, moleküler metalleri ve sıvı kristal renkli alan uygulamaları gibi yüksek teknolojik uygulamaları da her geçen gün artmaktadır. Sübstitüe olmayan ftalosiyaninler suda ve birçok organik çözücüde çözünmediklerinden son yıllarda yapılan çalışmaların önemi çözünür ürünler elde etme doğrultusunda olmuştur. Bu amaçla bu bileşiklerin çözünürlükleri periferal olarak hacimli sübstitüentlerle (örneğin SC^Na4", -NR.3+ vs.) ya da makro halkalarla (taç eter vs.) artmaktadır. Bu çalışmada ftalosiyaninin periferal konumlarına farklı substitüenlerin bağlanması amaçlanmıştır. Bu amaçla önce 4,5-dikloro- 1,2- disiyonobenzen dört kademede elde edilerek bu bileşiğin CS2CO3 ortamında 2-aminofenol ve 2-aminotiyofenol ile reaksiyonundan büyük oranda tek klor atomu nükleofilik sübstitüsyona uğramış olup ele geçen dinitril ürünleri saflaştırma metotlarıyla saflaştınlmıştır. IXÇalışmanın ikinci aşamasında periferal konumda farklı substitüenler taşıyan dinitril bileşikleri yüksek sıcaklık ve metal tuzlanyla ftalosiyaninlere dönüştürülmüştür (Ni, Zn, Co). Ftalosiyaninlerin uygun metodlarla saflaştırıldıktan sonra elemental analiz yanında İR, uv-vis, 1H NMR ve MS (kütle) spektrumlan yardımıyla yapılan aydınlatılmıştır.

SYNTHESIS OF PHTHALOCYANINES WITH DIFFERENT FUNCTIONAL SUBSTITUTENTS AND INVESTIGATION OF THEIR PROPERTIES KEYWORDS: Phthalocyanine, cobalt, nickel, zinc The complexes of porphyrins, corrins and phthalocyanines have been investigated because of relation to important naturally occuring species containing macrocycles such as, heme, cytocromes or chlorophyll or because of their potential as dyestuffs as pigments. Since their final discovery and elucidation of structure, phthalocyanine compounds have gained a real success as an object of research and of pratical application. The phthalocyanines find use also in catalysts for control of sulfur effluents, lasers, photodynamic reagents for cancer therapy, molecular metals, chemical sensors. An essential shortcoming of the phthalocyanines and structural analogues remained their low solubility in organic solvents which made difficult their application in solutions. The introduction into benzenic rings of the phthalocyanine molecule of voluminous sübstitüents (for example SOaNa+, -NR.3+ etc.) or (crown-ether) result in weaking of intermolecular interaction in the crystalline state and subsequently in a XIdrastic increase of solubility in organic solvent expecially non polar ones. Moreover, the introduction of various sübstitüents, such as amino, phenylthiogroups into benzerde rings turned out to be a powerful means of modifying the chemical and physical properties of the phthalocyanines. In the present work, we report here preperation and characterization of 4,5- differently sübstitüed phthalonitrile derivaties through CS2CO3 base-catalyzed nucleophilic aromatic displacement reaction in tetrahydrofuran solvent medium. In other word, the reaction route was applied to prepare 4-(2'-aminothiophenylsulfanyl) -5-chloro-l,2-dicyanobenzene (2a) and 4-(2'-aminophenoxy)-5-chloro-l,2- dicyanobenzene (2b) from the corresponding 2-aminotiophenol or 2-aminophenol and 4,5-dichloro-l,2-dicyanobenzene (Scheme 4.1 and Scheme 4.2). The reactions were carried out in tedrahyrofuran at room temperature with a low yield (% 20.57). The mixture of the crude products were seperated by using HPLC and purified. Cyclotetramerization of the 4-(2-aminothiophenylsulfanyl)-5-chloro-l,2- dicyanobenzene or 4-(2,-aminophenoxy)-5-chloro-l,2-dicyanobenzene derivative (2a and 2b) into the metallo phthalociyanine) (4a, 4b, 5a, 6a) were carried out in anhydrous metal salts (NİCI2, Zn(OAc)2 and C0CI2) and quinoline or ethyleneglycol. The desired metallo phthalocyanines were purified by column chromotography with silica gel. The elemental analysis, IR, ^-NMR, MS (mass) and Uv-Vis spectra confirm the proposed structures of the compounds. A diagnostic feature of the phthalocyanine formation from the cyano derivatives is the dissappearance of sharp intense C=N vibration bands of the reactants in the IR spectrum. The 'H-NMR spectra of the newly sythesized ligands and phthalocyanines in deutered DMSO gave rather broad peaks between 5-6 ppm, indicating the XIIappearence of the functional groups Ar-NH2 of the synthesized compounds while it dissappear by addition of D2O. Also, the doublet in the lower field of the H-NMR spectra can easily ascribed to the splitting of the benzene protons at the corner of phthalocyanines. Chemical shifts due to the Ar-NH2 two different Ar-H are the dominating signal in the spectra of the phthalocyanines. The UV-vis spectra (4a, 4b, 5a, 6a) in DMF show the intense Q-absorption bands above 600-700 nm. There is a shoulder at slightly higher energy side for the phthalocyanine compounds. The longer wavelength encountered for 4a-4b is expecially noteworth to donate shift of this intense band near IR region as a result of S-substitution. Mass spectra of the differently substituted phthonitriles and some phthalociyanines has confirmed the proposed structures. XIII