Yeni tip periferal ve nonperiferal tiyazol sübstitüye metaloftalosiyaninler
A new type peripherally and nonperipherally thiazol substituted soluable phthalocyanines
Yazar: EMİNE GÜLRUH DURUK
Danışman: PROF. DR. ZEHRA BAYIR
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Doktora, 2015
Konu: Kimya = Chemistry
Dizin: Metaloftalosiyaninler = Metallopthalocyanines ; Sübstitüe ftalosiyaninler = Substituted phtalocyanines

Özet:
Ftalosiyaninler 1907 yılında metalsiz olarak (H2Pc) 2-siyanobenzilamin hazırlığı sırasında kazara üretilmiş bileşiklerdir. Bu buluştan yirmi yıl sonra 1927 yılında Disbach ve çalışma arkadaşları tarafından 1,2-dibromobenzen'den yola çıkarak bakır ftalosiyaninler elde edilmiştir. Linstead ve çalışma arkadaşları sentetik metodları geliştirerek, metalli ftalosiyaninleri (MPc) sentezlemiş ve ftalosiyanin (Pc) yapılarını aydınlatmışlardır. Robertson tarafından ftalosiyaninlerin (Pcs) yapılarının X-ışını kırınımı analizi uygulanmıştır.
Ftalosiyanin ismi ilk kez Linstead tarafından kullanıldı. Ftalosiyaninler yapısal olarak doğada doğal olarak bulunabilen hemoglobin, klorofil ve B12 vitamini gibi porfirinlerin yapılarına benzer sentetik moleküllerdir. Tetrabenzotetraazaporfirinler ve 4 izo-indolinin tetramerizasyon ürünleri olarak kabul edilebilirler ve düzlemsel yapıda 18  elektron sisteminden oluşurlar. Çok kararlı mavi veya yeşil pigment ve boyalardır ve birçok teknolojik alanda ticari olarak önemli olarak sınıflandırılan kimyasallar olarak kullanılırlar.
Endüstriyel olarak CuPc ilk kez 1953 yılında bir İngiliz şirketi tarafından üretilmiştir ve daha sonra Almanya ve ABD'deki şirketler üretimini sağlamıştır. Bugün, yaklaşık 70 farklı elementi içeren metaller ve bazı metaloidlerin farklı çeşitlerde merkez atomu olarak kullanıldığı, periferal ve nonperiferal sübstitüye türevleri mevcuttur [1].
Kükürt ve azot taşıyan beşli bir halka sisteminin en önemli temsilcisi olan tiyazol molekülü oldukça kararlı olup, bazlığı çok zayıftır. Doğal bir halkadır ve tiyamininin (B1 vitamini) fonksiyonlu kısmını oluşturur. Penisilinde de tiyazolidin halkası bulunur. Beşli halkada bir kükürt ve bir azot atomu 1,3 yerinde bulunuyorsa "tiyazol"; 1,2 yerini içeriyorsa "izotiyazol" adını alır.
Tez kapsamında ftalosiyanin halkasına çözünürlük sağlayacak uygun sübstitüye gruplar bağlanarak, bu yapıların çeşitli metal tuzlarıyla metaloftalosiyaninleri hazırlanmıştır. Elektrokimyasal özellikleri ve redoks davranışları incelenmiş olan bu komplekslerin hidrojenin katalitik indirgenmesine olan elektrokatalitik aktiviteleri belirlenmeye çalışılmıştır. Bunun sonucunda sudan hidrojen üretiminde kullanabilecek, verimli ve aktif değişik hidrojen üretim sistemlerinin geliştirmesi için uygun yapılar elde edilmiştir. Kullanım amacına uygun, Co, Zn, Mn gibi redoks-aktif metalleri içeren, suyun potansiyel skalası içerisinde çoklu reversibl elektron transfer özelliklerine sahip olabilecek farklı ftalosiyanin kompleksleri sentezlenmiştir. Bu komplekslerin elektrokatalitik aktivitelerinin incelenmesi için öncelikle elektrokimyasal, spektroelektrokimyasal ve ince film özellikleri belirlenmiş ve elde edilen veriler ışığında uygun komplekslerin elektrokatalizör olarak kullanımları incelenmiştir.
Bu kapsamda, çalışmanın ilk kısmında nonperiferal pozisyonlarında tiyazol grupları taşıyan tetra sübstitüye simetrik metalli ftalosiyaninler (Zn, Mn, Co) sentezlenmiştir. İlk olarak, 6, 7, 8 numaralı nonperiferal 2-(4-metil-1,3-tiyazol-5-il)etoksi grubu ile sübstitüye kobalt, çinko ve magnezyum ftalosiyaninler sentezlenmiş ve karakterize edilmiştir. Metaloftalosiyaninlerin-hekzanol içinde DBU varlığında, metal tuzları ile birlikte (CoCl2, Zn(CH3COO)2, MnCl2) disiyano türevi 3'ün (3-[2-(4-metil-1,3-tiyazol-5-il)etoksi]ftalonitril) siklotetramerizasyonu sonucunda elde edilmiştir. Sentezlenen yeni ftalonitril bileşiklerinin ve ftalosiyaninlerin yapıları, elementel analiz, IR, UV-vis, 1H-NMR, 13C-NMR ve kütle spektroskopik teknikleri kullanılarak aydınlatılmıştır. Ayrıca, elde edilen 7 bileşiğinin elektronik absorbsiyonu ve floresans kuantum alanının içeren fotofiziksel özellikleri ve ayrıca gaz sensör özellikleri incelenmiştir.
Çalışmanın ikinci kısmında, 9, 10, 11 numaralı periferal 2-(4-metil-1,3-tiyazol-5-il)etoksi grubu ile sübstitüye kobalt, çinko ve magnezyum ftalosiyaninler sentezlenmiş ve karakterize edilmiştir. Bu ftalosiyaninler de n-hekzanol içinde DBU varlığında, metal tuzları ile birlikte (CoCl2, Zn(CH3COO)2, MnCl2) disiyano türevi 5'in (4-kloro-5-[2-(4-metil-1,3-tiyazol-5-il)etoksi]ftalonitril) siklotetramerizasyonu sonucunda elde edilmiştir. Sentezlenen yeni ftalonitril bileşiklerinin ve ftalosiyaninlerin yapıları, elementel analiz, IR, UV-vis, 1H-NMR, 13C-NMR ve kütle spektroskopik teknikleri kullanılarak aydınlatılmıştır.

Abstract:
Metal-free phthalocyanine (H2Pc) was obtained by accident for the first time in 1907 as a by-product during the preparation of 2-cyanobemzamide. Twenty years after this discovery, copper phthalocyanine was synthesized by Disbach and his coworker from 1,2-dibromobenzene in 1927. Linstead and his coworkers prepared several metallophthalocyanines (MPc) by developing synthetic methods and elucidated the structure of phthalocyanines (Pcs). X-ray diffraction analyses of them were performed by Robertson.
The name phthalocyanine was first used by Linstead. Pcs are synthetic macrocycles structurally similar to naturally available porphyrins such as hemoglobin, chlorophyll, and vitamin B12. They can be regarded as tetrabenzotetraazaporphyrins and as tetramerezitation products of 4 iso-indoline units and consist of a planar structure with an 18 π-electron system. They are very stable blue or green pigments and dyes, an important class of chemicals for commercial use in many areas of technology.
As a blue pigment CuPc was first produced industrially in 1935 by an English company and then other companies in Germany and the USA. Today, CuPc and peripherally or nonperipherally substituted derivatives, and about 70 different elements including metals and some metalloids have been used as central atoms in all kinds of Pcs [1].
Phthalocyanines have found a great number of important technological applications such as in non-linear opticdevices, dyes and pigments, catalysts, medical applications, chemical sensors, electrochromic devices and liquid crystals. In medicine, phthalocyanines have been found to have applications as phototoxic drugs for photodynamic therapy of cancer.
Aromatic heterocyclic compounds containing nitrogen and sulfur have important industrial uses. Thiazole, a five-membered ring heterocycle, is an important species of this type and enjoys widespread use for manufacturing biocides, fungicides, dyes and pharmaceuticals, treatment of inflammation, hypertension, bacterial and HIV infections. It is a liquid which smells like pyridine and the boiling point is 117°C. The molecules is considerably stable, on the other hand it is very weak as a base. It is the natural ring ve it is the functional group of the thiamine (B1 vitamin) and epothilone, a potent anti-cancer drug.
There is a thiazole ring in the penicillin structure. If the quintet ring is the place 1,3, the structure name is "thiazole", if the quintet ring is the place 1,2, the structure name is iso-thiazole. In general, thiazoles are well represented in biomolecules. Thiazoles are characterized by a larger delocalisation of the p-electrons than that obtained for the corresponding oxazoles and, therefore, possess superior aromatic character. The thiazole derivatives exhibit a wide range of importantbiological activities, including drugs in pharmaceutical industry; because of this reason we have planned to make an attempt toattach thiazole groups onto the Pc ring.
Within the scope of the thesis, the new type metalo phthalocyanines were prepared with the substituted thiazole groups which are providing solubility and with the different metal salts. Electrochemical speciality and redox behaviours is evaluated of the catalytic reduction of hydrogen for the new synthesized phthalocyanines complexes of were tried to defined electrocatalytic activities and including Co, Zn, Mn active metals that are redox active materials which are active, different and suitable for the aim of usage and has the multiple reversible electron transfer speciality were synthesized. Firstly, the new new synthesized phthalocyanines were defined electrochemical, spectrochemical and thin film specialities for being investigated of the electrocatalitic activities. In this way, it is planned that more productive and utilizable hydrogen production system modelling can be realized.
For this aim, first part of the studying the novel, symmetrical, nonperipherally tetrasubstituted metallophthalocyanines (cobalt, zinc, and manganese) bearing four 2-(4-methyl-1,3-thiazol-5-yl)ethoxy units were synthesized. Therefore, cyclotetramerizations of the dicyano-derivative (3) to the metallo-phthalocyanines (6-8) were accomplished in n-hexanol in the presence of DBU and metal salts (CoCl2, Zn(CH3COO)2, MnCl2). Elemental analyses and spectral data (EI-MS, MALDI-TOF, 1H-NMR, UV-Vis, and FT-IR) for all new products are consistent with the proposed structures.
Photophysical properties with zinc (II) (7) phthalocyanine were found, including electronic absorption and fluorescence quantum yield. The fluorescence of the complexes was investigated in DMF and it was found that benzoquinone (BQ) was an effective quencher. The response and recovery behaviours of the spin coated films to different analytes, which span a broad range of Lewis base, have been investigated by means of conductivity measurements. It was observed that the operating temperature had a considerable effect on the gas sensing performance of the sensors investigated. The sensing behaviour of the films for a broad range of Lewis bases and the correlation between the sensor sensitivity and Lewis base enthalpies were investigated. Results show that sensitivity of the films may be correlated exponentially with binding enthalpy.
In the second part of this study, the novel, symmetrical, peripherally octasubstituted metallophthalocyanines (cobalt, zinc, and manganese) bearing 2-(4-methyl-1,3-thiazol-5-yl)etoksi]ftalonitril) units were synthesized. Therefore, cyclotetramerizations of the dicyano-derivative (5) to the metallo-phthalocyanines (9-11) were accomplished in n-hexanol in the presence of DBU and metal salts (CoCl2, Zn(CH3COO)2, MnCl2). Elemental analyses and spectral data (EI-MS, MALDI-TOF, 1H-NMR, UV-Vis, and FT-IR) for all new products are consistent with the proposed structures.
Aggregation behaviors of phthalocyanines were investigated in different solvents. Redox properties of the complexes were determined with voltammetric and in situ spectroelectrochemical measurements. The Beer– Lambert law was obeyed for the compounds in DMF for the concentrations ranging from 4.00x10-6 to 14.00x10-6 M. Electrochemical and spectroelectrochemical measurements exhibit that the incorporation of the redox-active metal ions, CoII and MnIIIOAc, into the phthalocyanine core extends the redox richness of the Pc ring with the reversible metal-based reduction and oxidation couples in addition to the common Pc ring-based electron transfer processes. 
Assignments of the redox processes of the complexes were supported with in situ spectroelectrochemical measurements. Multi-electron and metal and Pc based redox properties of the complexes increase the worth of the complexes for the possible use as functional materials in various electrochemical applications, such as the fields of electrosensing, electrochromism, and electrocatalysis.