Substitüe yeni Ni(II) ve Zn(II) ftalosiyaninlerin sentezi
The synthesis of substitue new phthalocyanines Ni(II) and Zn(II)
- Tez No: 66777
- Danışmanlar: PROF. DR. ÖZER BEKAROĞLU
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Ftalosiyaninler, Nikel, Çinko, Phthalocyanines, Nickel, Zinc
- Yıl: 1997
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: İnorganik Kimya Bilim Dalı
- Sayfa Sayısı: Belirtilmemiş.
Özet
ÖZET Ftalosiyaninler genellikle ftalonitril, ftalikanhidrit, ftalimid veya bunlann substitüsyon ürünleri ile metal tuzlan arasındaki reaksiyonlardan elde edilebilen ve genellikle güç çözünen bileşiklerdir. Bu yüzden ftalosiyanin kimyasındaki önemli bir hedef de çözünür ürünler elde etmektir. Bu bileşiklerin çözünürlükleri, periferal olarak hacimli substitüentler, (örneğin; -t- Bu, -C^H^, -OC12H25), polar gruplar (-SQNa, -NR^) veya makro-halkalar ilavesiyle artırılabilmektedir. Taç eter, monoaza ve tetraazamakrohalkaları İçeren ftalosiyaninlerin sentezi ve incelenmesi grubumuz tarafından yapılan çalışmaların büyük bir bölümünü oluşturmaktadır. Ftalosiyaninlerin boya, optik ve elektriksel malzemeler olarak ticari kullanım alanlarının yanında, fotodinamik kanser tedavisi, yakıt pilleri, kimyasal sensör, solar enerji gibi yüksek teknolojik kullanım alanlarına uygulamaları her geçen gün hızla artmaktadır. Çalışmamızda 4,5-dikloro-l,2-disiyanobenzenden yola çıkarak 1,2- disiyano^Wıkiroksi-5-hidroksietil sülfanil türevi elde edilmiştir. Bu ftalonitril türevinden susuz metal tuzları ile (NiCl2, Zn(OAc)z ) bu tuzlara karşı gelen, metalli ftalosiyaninler sentezlenmiştir. Yeni sentezlenmiş ftalosiyaninlerin yapılan; elemental analiz, İR, UV/VIS ve NMR gibi spektral yöntemlerle aydınlatılmıştır. -vi-
Özet (Çeviri)
SUMMARY THE SYNTHESIS OF SUBSTITUE NEW PHTHALOCYANINES Ni(II) AND Zn(H) The phthalocyanine moiety is a synthetic maerocycle (Fig. 1 : M=H2) that is related to natural products like porphyrins. Phthalocyanine and metallophthalocyanines have been investigated in detail for many years especailly with regard to their properties as dyes. Since the last 20 years, phthalocyanine chemistry is undergoing a renaissance, because phthaloacyanines and many of its derivatives exhibrit properties mat are interesting for application in material science. Figure 1. Phthalocyanine Up to now, about 70 different elements were used as central atoms in phthalocyanine, naphmalocyanine, and similar macrocycles (Fig.2) controlling thereby not only the thermal stability, but also, for example, the oxidation potential of the phthalocyaninato- and naphthalocyaninato element compounds. The oxidation potential is an important factor for the electrical properties of metallomacrocycles. Generally, peripherally unsubstituted phthalocyanines are not soluble in organic solvents or in water, only in H2S04, which often leads to sulfanation. -Vll-PhcM AncM TBPM N' N ?0 NMN N^ M HpM <£-> Figure 2. Macrocycles: 1,2-NcM, 1,2-metallonaphthalocy anine; 2,3-NcM, 2,3- metallonaphthalocyanine; PhcM, metallophenantrenocyanine; AncM, metalloanthracenocyanine; TBPM, metallotetrabenzoporphyrin; and HpM, netallohemiporphyrazine. Although the special nature of phthalocyanines and their metal complexes have been known for about 60 years, their uses as commercial dyes, catalysts, optical and electrical materials are expanding enormously every year. -Vlll-In recent times, the compelling reason for studying the detailed coordination chemistry of metallophtalocyanines has arisen. The great activity in bioinorganic chemistry has led to verifiable avalanche of work on metalloporphyrins and other naturally occuring macrocyclic coordination compounds. Thus, the metallophthalocyanines have been examined so far and their properties are compared to those of the porphyrin complexes in the hopes of arriving at an understanding of how the naturally occuring macrocyclic porphyrin ligand affects the properties of the metal. The rich coordination chemistry of phthalocyanine complexes has encouraged researchers to“tailor”specific products with certain properties which are required for high-technology applications. The two variables are the central metal ion and the peripheral substiruentsrwhen there is the possibility of inserting a great number of different metal ions which are combined with the unlimited number and type of substituents into the phthalocyanine core, the possibility of obtaining novel products is infinite. In addition to their extensive use as dyes and pigments, phthalocyanines have found wide applications in the Mowing areas in catalysis, optical recording, photoconductive materials, photodynamic therapy and also as chemical sensors. For this wide range of applications, the stable phthalocyanine 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. Metallophthalocyanine have been used as photocatalysts or electrocatalysts in the reduction of methyl viologen, the reduction of oxygen of water and the reduction of carbondioxide. In the latter one, carbondioxide is reduced in many aqueous solutions to formic acid. In aprotic solvents, carbonmonoxide or oxalic acid is formed, but in aqueous solutions containing tetraalkylammomum salts, reduction to oxalic acid followed by further reduction to glyoxylix acid is observed and the products depend strongly on the proticity of the solvent The results of the interaction of carbondioxide with metal phthalocyanines have also been reported. One of the important aims of research on the chemistry of phthalocyanines is to enhance their solubility in various solvents. While peripheral substitution with bulky groups or long alkyl chains leads to phthalocyanine derivatives soluble in common organic solvents, the -IX-introduction of sulphonyl, carboxyl or amino groups results in water-soluble products. There are several methods of preparing phthalocyanines, depending on the starting materials. Phthalocyanines and its metallated derivatives have been purified by sublimation and by dissolution in concentrated sulphuric acid followed by precipitation on ice. The extreme insolubility of most phthalocyanines makes the usual recrystallization, extraction or chromatographic methods inapplicable. In this study, firstly, l,2-dicyano-4-hydroxy-5-hydroxyethylsulfanyl- benzene 2, was obtained by the reaction of 2-mercaptoethanol with 4,5- dichloro-l,2-dicyanobenzene. (Scheme 1). The reaction was carried out in anhydrous dimemylformamide at 40°C with a yield of 64 %. HO 1 SH DMF K2C03 Scheme 1. l^-dicyano-4-hydroxy-5-hydroxyethylsulfanyl-benzene Secondly, Ni(H) phthalocyanine, 3 was obtained by the reaction of 1,2- dicyano-4-hydroxy-5-hydroxyethyl sulfanyl with anhydrous NiCl2 in dry dimethyl formamide at 180°C-190°C for approximately 22 hours under nitrogen atmosphere (Scheme 2). Since, Ni(II) phmalocyanine 3, is not soluble in number of organic solvents such as ethanol and DMF, the impurities are seperated from the yield by boiling it with ethanol and DMF at 80°C and then filtering the reaction mixture including the phthalocyanine. Zn(n) phthalocyanine 4 was also obtained in a similar method used for producing the Ni(II) phthalocyanine (Scheme 2). To obtain the Zn(H) phthalocyanine, 4, l,2-dicyano-4-hy<iroxy-5-hydroxyethylsulfanyibenzene was reacted with dry Zn(OAc)2 in anhydrous DMF at İ8Ö°C-190ÖC for about 20 hours. -X-OH S 3 3 4 M=Ni M=Zn Scheme 2. Synthesis of Ni(II) phthalocy anine and Zn(H) phthalocyanine. Zn(II) phthalocyanine 4 is soluble in DMF, DMSO and pyridine; whereas Ni(IT) phthalocyanine 3 is only slightly soluble in pyridine. IR spectrum of l^^ficyano^hydroxy-S-hydro^ethylsulfanylbenzene 2, indicates the presence of alkyl and cyano groups by the intense characteristic strectging bands of C-H around 2970-2950 cm“1 and ON at 2230 cm”'. The latter has disappeared after conversion of 2 to 3 or 4. -XI-In the 'H-NMR spectrum of 2, aromatic protons appear as a singlet at 7.16 ppm and 7.80 ppm. (S-CH2) protons come out as a triplet at 3.14 ppm, (0-CH2) protons appear as triplet at 3.67 ppm and phenolic (O-H) proton appears as a singlet at 1 1.7 ppm. In the "C-NMR (APT) spectrum of 2, the C-atoms belonging to (-ON) group give signals at 1 16.31 and 1 16.06 ppm. C-atoms of (-CH2S) group give a signal at 32.48 ppm. Moreover, the aromatic C-atoms give signals at 105.16, 110.78, 117.21, 129.94, 133.80 and 157.40 ppm. Additionally, the C-atom belonging to (-CH20) group gives a signal at 59.27 ppm. The LTV/VIS spectra of the phthalocyanine, 3 in pyridine shows the intense Q band absorption at 696 nm. Likewise, tihe VIS spectra of the phthalocyanine, 4 in DMF shows the intense Q band absorption at 698 nm. -Xil-
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