Taç eter substitue yeni ftalosiyaninler
Novel phthalocyanines with crown ether substituents
- Tez No: 39765
- Danışmanlar: PROF.DR. ÖZER BEKAROĞLU
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1994
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 71
Özet
ÖZET Ftalosiyaninler genellikle ftalonitril ve bunların çeşitli türevlerinden (örneğin ftalimid, ftalik asit vb.) metalsiz olarak ve metal tuzlanyla tercihen yüksek sıcaklıklarda metalli olarak elde edilmektedirler. Ayrıca o-pozisyonunda halojen içeren çeşitli aromatik bileşikler de CuCN ile reaksiyona sokulursa ftalosiyanin oluşmaktadır. Elde edilen ftalosiyaninler genellikle mavi renkli, yüksek ısıya ışığa ve asitlere karşı dayanıldı, fakat çözünürlüğü çok az olan bileşiklerdir. Bu çalışmada organik solventlerde çözünebilen ftalosiyanin sentezi için yeni bir başlangıç maddesi olan l-{([Benzo-15-crown-5]-4'yl)tiya}-3,4-disiyano benzen (1) sentezlenmiş ve buradan da ilgili metal tuzlanyla yeşil renkli nikel, kobalt, balar, çinko, kurşun, kalay (kahverengi) ve hidrokinonla metalsiz ftalosiyaninler elde edilmiş, ayrıca Nikel ftalosiyaninden yapılan Palladyum kompleksi denemesi de başarılı olmuştur. Elde edilen yeni maddelerin yapılan Elementel Analiz, İR, UV/Vis ve NMR yöntemleriyle aydınlanmıştır.
Özet (Çeviri)
SUMMARY NOVEL PHTHALOCYANINES WITH CROWN ETHER SUBSTITUENTS Since their early synthesis this century, phthalocyanines have established themselves as blue and green dyestuffspar excellence. They're an important industrial commodity (output 45.000 tons in 1987) used primarily in inks (especially ballpoint pens), coloring for plastics and metal surfaces, and dyestuffs for jeans and other clothing. More their use as the photoconducting agent in photocopying machines heralds a resurgence of interest in these species. In the coming decade, their commercial utility is expected to have significant ramifications. Thus future potential uses of metal phthalocyanines, currently under study, include 1) Sensing elements in chemical sensors. 2) Electrochromic display devices. 3) Photodynamic reagents for cancer therapy and other medical applications. 4) Applications to optical computer read/write discs, and related information storage systems. 5) Catalysts for control of sulfur effluents 6) Electrocatalysis for fuel cell applications. 7) Photovoltaic cell elements for energy generation 8) Laser dyes 9) New red sensitive photocopying applications 10) Molecular metals and conducting polymers. In addition to their extensive use as dyes and pigments, phthalocyanines have found wide applications in catalysis, in optical recording, in photoconductive materials, in photodynamic therapy and as chemical sensors. For this broad range of applications the stable phthalocyanines core should be amenable to modifications which can be accomplished either by changing the central metal ion or by adding functional groups on the periphery. By a judicious choice of substituents with suitable donor groups on the periphery, one can direct the phthalocyanine interactions with metal ions or with one another; the -vi-consequences of these phenomena will appear in affecting the ordering of molecular assemblies in the solid state as well as in solution. Drastic changes occur in the absorption spectra and photophysical properties when strongly conjugated macrocycles such as phthalocyanines are forced to lie in face-to-face conformations. Although phthalocyanines with N- and O-donor substituents have been frequently encountered, those with thioether moieties are rather few. The latter group contains essentially products obtained by the cyclotetramerization of thioether substituted phthalonitriles which themselves have been derived by nucleophilic displacement reactions of dinitriles. Physical and chemical properties of soluble phthalocyanines have recently "attracted much attention from material chemists for their potential use in semiconducting materials, nonlinear optics and,, other optical devices. At the same time, since they effectively absorb in the lower energy region of visible light, they have found extensive application as photoconductors in optical recording materials as well as photosensitizers in photodynamic therapy. The advantage of using soluble phthalocyanines for these applications, incontrast to the insoluble parent phthalocyanines, is the possibility to reach high purification degrees by column chromatography or crystallization. Incorporation of macrocyclic groups such as crown ethers, tetraaza or diazatrioxa macrocyle onto the periphery of phthalocyanines has enhanced the solubility of these compounds. At the same time, additional binding sites for different kinds of ions have been provided. The macrocyclic substituents also bring about novel features such as ion channel and mesophase formation when the macrorings are integral parts of the inner core by way of enhancing the planarity of the molecules. A flexible bridging group between the core and the macro-substituents, on the other hand, provide the possibility of intramolecular or intermolecular interactions of macrocyclic groups as encountered with tetra- or octa- (oxymethylbenzo-15-crown-5) substituted phthalocyanines. As part of our continuing interest in synthesizing novel compounds carrying multi-donor sites suitable for binding different ions at the same time we have synthesized a new phthalocyanine carrying four benzo-15-crown-5 substituents through thioether bridges. It is also expected to be a new contribution to the thia-substituted phthalocyanines which are rather few in the literature and which recently receives interest for the shift of their intense Q absorptions to the longer wavelengths. At the same time, alkali ion binding properties of the crown ether substituents will be evaluated in comparision with the similar compounds. -vu-In the present work, we., have synthesized for the first time l-{[(benzo-15- crown-5)-4'yl]thia}-3,4-dicyanobenzene (1). The key step of the synthetic route to prepare phthalocyanines carrying thia-bridged benzo-15-crown-5 moieties relied upon the well-known base-catalyzed aromatic nitro displacement of 4- nitrophthalonitrile with 4'-mercapto-benzo-15-crown-5, which was also itself obtained through a multi-step reaction. Anhydrous ^COj was the base of choise and DMSO was the solvent. The reaction was made to proceed by us- ing the carbonate ion as the nitro-displacing nucleophile. (Scheme 1)
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