Publication: 1,1'-tiyobis (naftalen-2-oksi) grubu içeren diftalonitril bileşiklerinden metalli ve metalsiz ftalosiyaninlerin sentezi ve karakterizasyonu
Abstract
Ftalosiyaninler, içerdiği 18 π eletronunun halkadaki rezonansı sonucu yüksek kararlılığa sahip makromoleküllerdir. Periferal(karşı) ve non-perferal(karşı olmayan) pozisyonlarındaki sübstitüentlerin (grupların) ve merkezlerindeki ‘oyuk’ olarak tabir edilen boşluğa yerleşebilecek metal iyonlarının çeşitliliği sayesinde gösterdikleri fiziksel ve kimyasal özellikleri değiştiğinden kullanım alanları hızla genişlemiştir. Ftalosiyaninler, günümüzde güneş pilleri, kimyasal sensörler, non-lineer optik araçları, elektro-kromik görüntüleme cihazları, kanserin fotodinamik terapi ajanları ve sıvı-kristal ekranlar gibi ileri teknoloji uygulamalarında sıklıkla kullanılan makromoleküllerdir. Bu çalışmada; 1,1-tiyobis(naftalen-2-ol) ve 3-nitroftlaonitril susuz sodyum karbonat kuru dimetilformamit (DMF) içinde 50°C’ de 60 saat ısıtılarak karıştırıldı ve nükleofilik aromatik sübstitüsyon reaksiyonu ile 3,3'((tiyobis(naftalene-1,2-diil))bis(oksi)) diftalonitril başlangıç bileşiği elde edildi. Benzer şekilde 1,1-tiyobis(naftalen-2-ol) ve 4-nitroftalonitril kullanılarak 4,4'-((tiyobis(naftalene-1,2-diil))bis(oksi))diftalonitril başlangıç bileşiği elde edildi.Bu başlangıç bileşikleri kullanılarak metalsiz ve farklı merkezi metal (Cu(II), Fe(II), Mn(II) (top tipi binükleer Pc’lerde Mn(III)), Ni (II)) iyonları içeren mono ve dinükleer (top tipi binükleer) ftalosiyanin kompleksleri sentezlendi. Başlangıç bileşikleri ve sentezlenen ftalosiyaninlerin karakterizasyonları 1H-NMR, 13C-NMR, UV-vis, FT-IR ve MALDI-TOFF yöntemleri kullanılarak yapılmıştır.
Phthalocyanines are macromolecules with the resonance with18 π electrons and thus high chemical stability. When the variety of the substituents (groups) in the peripheral (opposite) and non-peripheral (non-opposite) positions and the variety of metal ions that can settle in the 'hole' in their centers have been altered; their physical and chemical properties also change. Thus their usage areas expand rapidly. Phthalocyanines are macromolecules that are frequently used in advanced technology applications such as solar cells, chemical sensors, non-linear optics, electro-chromic imaging devices, photodynamic therapy agents of cancer, and liquid-crystal displays.In this study; 1,1-thiobis(naphthalen-2-ol), 3-nitrophthalonitrile and anhydrous sodium carbonate were stirred in dry dimethylformamide (DMF) by heating at 50°C for 60 hours and 3,3'-((thiobis(naphthalene-1,2-diyl))bis(oxy))diphthalonitrile starting compound was obtained. Similarly, the starting compound 4,4'-((thiobis(naphthalene-1,2-diyl))bis(oxy))diphthalonitrile was obtained using 1,1-thiobis(naphthalen-2-ol) and 4-nitrophthalonitrile. The classical mononuclear and dinuclear ball type phthalocyanines with metal-free and metallo (Cu, Fe, Mn and Ni) were synthesized by using these starting compounds. Characterizations of starting compounds and phthalocyanine complexes were performed using 1H-NMR, 13C-NMR, UV-vis, FT-IR and MALDI-TOF mass spectroscopies.
Phthalocyanines are macromolecules with the resonance with18 π electrons and thus high chemical stability. When the variety of the substituents (groups) in the peripheral (opposite) and non-peripheral (non-opposite) positions and the variety of metal ions that can settle in the 'hole' in their centers have been altered; their physical and chemical properties also change. Thus their usage areas expand rapidly. Phthalocyanines are macromolecules that are frequently used in advanced technology applications such as solar cells, chemical sensors, non-linear optics, electro-chromic imaging devices, photodynamic therapy agents of cancer, and liquid-crystal displays.In this study; 1,1-thiobis(naphthalen-2-ol), 3-nitrophthalonitrile and anhydrous sodium carbonate were stirred in dry dimethylformamide (DMF) by heating at 50°C for 60 hours and 3,3'-((thiobis(naphthalene-1,2-diyl))bis(oxy))diphthalonitrile starting compound was obtained. Similarly, the starting compound 4,4'-((thiobis(naphthalene-1,2-diyl))bis(oxy))diphthalonitrile was obtained using 1,1-thiobis(naphthalen-2-ol) and 4-nitrophthalonitrile. The classical mononuclear and dinuclear ball type phthalocyanines with metal-free and metallo (Cu, Fe, Mn and Ni) were synthesized by using these starting compounds. Characterizations of starting compounds and phthalocyanine complexes were performed using 1H-NMR, 13C-NMR, UV-vis, FT-IR and MALDI-TOF mass spectroscopies.