16-üyeli diazaditia-makrohalkaları içeren yeni tip ftalosiyaninler /
Yazar: İSMAİL YILMAZ
Danışman: PROF.DR. ÖZER BEKAROĞLU
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü
Derece: Doktora, 1996
Konu: Kimya = Chemistry
Dizin: Ftalosiyaninler = Phthalocyanines

Özet:
ÖZET Ftalosiyaninler gösterdikleri özellikler sebebiyle geniş uygulama alanlarına sahip olan çok kararlı bileşiklerdir. 20.Yüzyılın başlarında bulunan ftalosiyaninler uzun yıllar pigment ve boyar madde olarak kullanılmışlardır. Ftalosiyaninler genellikle güç çözünen bileşiklerdir. Bu bileşiklerin çözünürlükleri; hacimli substituentler, polar gaıplar veya makro halkalar ilavesiyle artınlabilmektedir. Bu sayede, kimyasal ve fiziksel özelliklerinde değişiklikler meydana getirilerek yapıların incelenebilmesine de imkan sağlanabilmektedir. Bu çalışmada 2-aminotiyofenol ve l,2-Dibromo-4,5 bis (bromometil) benzenden yola çıkılarak 1,2-bis (2'-aıninofeniltiometil)benzen elde edildi. Bu maddenin p-toluen sulfonil klorür ile tosillenmesiyle elde edilen maddenin 4,5-dibromo-o-ksilen ile reaksiyonundan 16-üyeli diazaditia makrosiklik halka elde edilmiştir. Dibrom türevi üzerinden bakır ftalosiyanin, dinitril türevi üzerinden de, (Ni(ll), Co(II)) ftalosiyaninler elde edilmiştir. Ayrıca, nikel ftalosiyaninde azot atomlarına bağlı tosil gaıplan kesilerek 12 adet sülfonat grupları taşıyan pentanükleer ftalosiyanin sentezi de gerçekleştirilmiştir. Elde edilen yeni maddelerin yapılan; Elementel analiz, ÎR, UV-VIS, NMR, MS spektrumlan ve atomik absorbsiyon ölçümleri ile aydınlatılmıştır.

Abstract:
SUMMARY NEW PHTHALOCYANINES SUBSTITUTED WITH FOUR 16-MEMBERED DIAZADITHIA MACROCYCLES The complexes of transition metals with various ligands are known since Werner. The stable complexes of the ınacrocyclic polyethers with alkali and alkaline-eaılh metal salts are important subject of intensive investigations since the work of pedersen in 1967. Pedersen prepared more than 60 compounds in order to ascertain the optimum ring size and the preferred constitational arrangement of oxygen atoms in the macrocycles for them to complex with a wide variety of cationic species. The study of the properties and syntheses of ınacrocyclic complexes may have important consequences for biochemistry since many important compounds in living systems, such as chlorophyl, hemoglobin ete., contain ınacrocyclic porphyring rings attached to metal atoms. The biosynthesis of these compounds probably in values soıne form of template synthesis. A groııp of related compounds, the phthalocyanines, are isoelectronic with porphyrins. They are interest not only as a model compounds tor the biologically important, porphyrins but also the commercially important intensively coloured metal complexes ad dyes and pigments Phthalocyanines are macrocylic molecules containing four isoindole units, which are synthetic analogs of naturally occuring porphyrins derived from the porphyring system. The first synthesis of a phtholocyanine was recorded in 1907 when Braun and Tscherniac heated o-cyanobenzamide at high temperature. The structure of this ınetal-free, unsubstituted phthalocyanine was determined only about a quarter of centuıy later by the comprehensive researches of Linstead and x-ray difîraction analyses of Robertson, while examining both metal-free phthalocyanine and metallophthalocyanines. Phthalocyanines are widely used as pigments and dyes. Various other properties for new applications were investigated in the last decade: Photodynamic activity in the photodynamic cancer therapy, photosensitization in solution, electrocatalysts for the dioxygen reduction in ftıel celi, electrochromic processes as thin films, photoreductions ör photooxidations in photo electrochemical cells, materials for electrophotography, optical information storage system, catalysts for mercaptan oxidations and use as sensors. A common prerequisite for most of these applications above mentioned is solubility in practical solvents. Additional factors, such as thermal stability, electrical conductivity and viiiÖZET Ftalosiyaninler gösterdikleri özellikler sebebiyle geniş uygulama alanlarına sahip olan çok kararlı bileşiklerdir. 20.Yüzyılın başlarında bulunan ftalosiyaninler uzun yıllar pigment ve boyar madde olarak kullanılmışlardır. Ftalosiyaninler genellikle güç çözünen bileşiklerdir. Bu bileşiklerin çözünürlükleri; hacimli substituentler, polar gaıplar veya makro halkalar ilavesiyle artınlabilmektedir. Bu sayede, kimyasal ve fiziksel özelliklerinde değişiklikler meydana getirilerek yapıların incelenebilmesine de imkan sağlanabilmektedir. Bu çalışmada 2-aminotiyofenol ve l,2-Dibromo-4,5 bis (bromometil) benzenden yola çıkılarak 1,2-bis (2'-aıninofeniltiometil)benzen elde edildi. Bu maddenin p-toluen sulfonil klorür ile tosillenmesiyle elde edilen maddenin 4,5-dibromo-o-ksilen ile reaksiyonundan 16-üyeli diazaditia makrosiklik halka elde edilmiştir. Dibrom türevi üzerinden bakır ftalosiyanin, dinitril türevi üzerinden de, (Ni(ll), Co(II)) ftalosiyaninler elde edilmiştir. Ayrıca, nikel ftalosiyaninde azot atomlarına bağlı tosil gaıplan kesilerek 12 adet sülfonat grupları taşıyan pentanükleer ftalosiyanin sentezi de gerçekleştirilmiştir. Elde edilen yeni maddelerin yapılan; Elementel analiz, ÎR, UV-VIS, NMR, MS spektrumlan ve atomik absorbsiyon ölçümleri ile aydınlatılmıştır.SUMMARY NEW PHTHALOCYANINES SUBSTITUTED WITH FOUR 16-MEMBERED DIAZADITHIA MACROCYCLES The complexes of transition metals with various ligands are known since Werner. The stable complexes of the ınacrocyclic polyethers with alkali and alkaline-eaılh metal salts are important subject of intensive investigations since the work of pedersen in 1967. Pedersen prepared more than 60 compounds in order to ascertain the optimum ring size and the preferred constitational arrangement of oxygen atoms in the macrocycles for them to complex with a wide variety of cationic species. The study of the properties and syntheses of ınacrocyclic complexes may have important consequences for biochemistry since many important compounds in living systems, such as chlorophyl, hemoglobin ete., contain ınacrocyclic porphyring rings attached to metal atoms. The biosynthesis of these compounds probably in values soıne form of template synthesis. A groııp of related compounds, the phthalocyanines, are isoelectronic with porphyrins. They are interest not only as a model compounds tor the biologically important, porphyrins but also the commercially important intensively coloured metal complexes ad dyes and pigments Phthalocyanines are macrocylic molecules containing four isoindole units, which are synthetic analogs of naturally occuring porphyrins derived from the porphyring system. The first synthesis of a phtholocyanine was recorded in 1907 when Braun and Tscherniac heated o-cyanobenzamide at high temperature. The structure of this ınetal-free, unsubstituted phthalocyanine was determined only about a quarter of centuıy later by the comprehensive researches of Linstead and x-ray difîraction analyses of Robertson, while examining both metal-free phthalocyanine and metallophthalocyanines. Phthalocyanines are widely used as pigments and dyes. Various other properties for new applications were investigated in the last decade: Photodynamic activity in the photodynamic cancer therapy, photosensitization in solution, electrocatalysts for the dioxygen reduction in ftıel celi, electrochromic processes as thin films, photoreductions ör photooxidations in photo electrochemical cells, materials for electrophotography, optical information storage system, catalysts for mercaptan oxidations and use as sensors. A common prerequisite for most of these applications above mentioned is solubility in practical solvents. Additional factors, such as thermal stability, electrical conductivity and viiian intermediate step in the phthalocyanine formation. The reaction of 4 in high-boling aprotic solvent, such as quinoline with the appropriate metal salts gave the monomelic phthalocyanines 6-9 (M=Ni", Co ). The yields of the products are veiy low, as encountered for phthalocyanines with other bulky groups. The most obvious feature of complex 5, 6 and 9 is their high solubility in common organic solvents, e.g. chloroform, dichloromethane, THF, DMSO, N,N-dimethyl- formamide (DMF), etc. Complexation experiments for phthalocyanines containing four 16-membered diazadithia macrocycles were carried out with both transition and alkali- metal ions, but no binding was indicated in the case of N-tosylated phthalocyanines which does not provide appropriate donor groups on the macrocycles. Detosylation of complex 6 was accomplished only in concentrated sulfuric acid at 125°C for 5h, although other detosylation methods under milder conditions had been tried. Also, longer reaction times and higher temperatures resulted in decomposition of the phthalocyanine derivatives. However, detosylation with sulfuric acid leads to a product with sulphonyl groups on the aromatic ring of the macrocycle which is a mixture of regioisomers. All attempts to separate these isomers by chromotographic techniques were not successful, but their presence could be verified by the slight broadening encountered in absorption bands of the 'H-NMR and electronic spectra when compared with those of octasubtituted phthalocyanines composed of a single isomer. The elemental analysis results indicate the presence of twelve-SO?H groups for each phthalocyanine along with four H2SO4 bound to the aza functions. Addition of these polar groups gave phthalocyanine which is extremely soluble in water. Neutralization of four H2S04 bound to the aza function and complexation experiment of four diazadithiamacrocycles to obtain pentanuclear complex was simultaneously accomplished by reaction of phthalocyanine subtituted sulphonyl groups on the aromatic ring of macrocycle 7 with CuCK in solution of 2 M NaOH in water at reflux temperature. Dark-blue product obtained was verified by elemental analysis to indicate a 1 :4 (7:Cuu) ratio as a consequence of encapsulation of one metal ion by each diazadithia macrocycle. In this pentanuclear complex, their highly ionic character was indicated clearly by their solubility in water. Elemental analysis results and the spectral data ('H-NMR, 1R and UV-VIS) for all the new products were consistent with the assigned formulations. Comparison of the 1R spectral data of 3 and 4 clearly indicates the conversion of the aromatic bromo groups into cyano derivatives by the disapperance of the C-Br band at 640 cm'1 in 3 and the apperence of a new C°N band at 2220 cm"1 in 4. The rest of the spectrum is closely similar to that of 4 including the characteristic vibrations of tosyl groups. Detosylation is verified by changes in the S02 stretches around 1370 and 1 150 cm" 1 for the tosylated compounds and 1 100, 1220 cm"1 for the sulpho products. The band around 3250 cm"1 for 8 can be attributed to the NH streching frequency. Also, the characteristic absorption of sulphate anion can be differentiated between 6 and 7 (1 100, 1220 cm"1). In the pentanuclear complex 8, intense absorptions due to this anion of 1 100- 1220 cm"1 observed. XIThe 'H-NMR spectra are also consistent with the proposed structures. In addition to the aromatic protons in diazadithiamacrocycles 3-4, CHt-N and CH2-S protons appear at 4.45, 4.15 ppm, respevtively. 'H-NMR investigations of metal phthalocyanines 6 and 7 have provided the characteristic chemical shifts for the staictures expected. An evident difference between the proton NMR spectra of 6 and 7 are the broad absorption encountered in the case of 7, which is both the result of the presence of ammonium groups on the aza functions of macrocycles of phthalocyanine and aggregation of phthalocyanine which is frequently encountered at the concentration for NMR measurements. 'H-NMR measurements were precluded owing to the paramagnetic nature of the copper (II) phthalocyanine 9 and pentanuclear complex 8. Phthalocyanines 16-membered diazadithia maxcrocycles 3-5 show typical electronic spectra with two strong absorption regions, one of them in the visible portion al 600-700 nm (Q-band) which has been attributed to the ti-k transition from the HOMO (Highest Occupied Molecular Orbital) to the LUMO (Lowest Unoccupied Molecular Orbital) of the Pc"2 ring, and the other in the UV region about 300-350 nm (B band) which has been attributed to the deeper p levels-» LUMO transition. In extremely dilute solution (ca 10"6 mol.dm"3), the molecules are present as monomers in dichloromethane. Increasing the concentration leads to aggregation which is easily monitored by the position of the Q-band which shift to shorter wavelengths and decreases in molar absorption coefficient. The sulphonated product obtained after detosylation show aggregation even at very low concentrations. The Q-bands shift 40-45 nm to higher energy from 6 to 7 and 8 which are consistent with the result obtained previously in similar phthalocyanines with sulphonated 1 7-membered diazatrioxa macrocycles. Of course the solvent effect should also be taken into account, 7 and 8 are soluble in water. Complexation of four diazadithia macrocycles with Cun did not lead to appreciable changes in the Q-band region in water, as expected from the low-intensitiy d-d transition. xn