Alkiltiyo- Ve Alkiniltiyo-sübstitüe Ftalosiyaninler
Alkiltiyo- Ve Alkiniltiyo-sübstitüe Ftalosiyaninler
Dosyalar
Tarih
2013-08-12
Yazarlar
Kaipova, Saida
Süreli Yayın başlığı
Süreli Yayın ISSN
Cilt Başlığı
Yayınevi
Fen Bilimleri Enstitüsü
Institute of Science and Technology
Institute of Science and Technology
Özet
Ftalosiyaninler (Pc) iki boyutlu 18 π-elektron aromatik porfirin sentetik analoglarıdır. Azot atomlarıyla birbirine bağlanmış dört izoindol temel ünitesi içerirler. Daha çok boya ve pigment hazırlanmasında kullanılan ftalosiyaninler, son yıllarda ayrıca elektronik ve optoelektronikte yeni moleküler materyallerin hazırlanmasında yapı taşı olarak da kullanılabilmelerinden dolayı ilgi çekmektedirler. Ftalosiyaninlerin elektron delokalizasyonundan kaynaklanan çeşitli özellikleri, onları bilim ve teknolojinin değişik alanlarında değerli kılmaktadır. Son zamanlarda sübstitüe ftalosiyaninler çok hızlı gelişmektedir. Çünkü bu gibi kromoforlar materyal biliminde özellikle fotodinamik kanser terapi, non lineer optik, sinyal belirleme tekniklerinde uygulama imkanı bulan eşsiz fizikokimyasal özelliklere ve gelişmiş organizasyon kabiliyetine sahiptirler. Periferal ve nonperiferal pozisyonlara çeşitli sübstitüentlerin eklenmesiyle ftalosiyaninlerin özellikleri değiştirilebilir. Sübstitüe olmamış ftalosiyaninler delokalize π elektron sistemlerinden dolayı üst üste istiflenerek çözünmez hale gelirler ve bu durum ftalosiyaninlerin işlenebilirliğini, türevlendirilmesini ve karakterizasyonunu kısıtlar. Hacimli grupların ligandın periferal konumlarına yerleştirilmesi ile π sisteminin moleküller arası etkileşimi azaltılarak ftalosiyaninlerin çözünürlüğü arttırılabilir. Bu nedenle alkil, alkiltiyo ve diğer fonksiyonel grupları taşıyan çok sayıda ftalonitril bileşiği sentezlenmiş ve siklotetramerizasyon reaksiyonlarında kullanılmıştır. Son on yılda, çok sayıda mono- ve poli-alkinil grubu içeren Pc sistemi, alkinil-sübstitüe ftalonitrillerin siklotetramerizasyonunu ve alkinil-içeren grubun önceden hazırlanmış Pc makrohalkasına metal katalizli kapling reaksiyonuyla yerleştirilmesini içeren iki temel stratejiye dayanılarak sentezlenmiştir. Bununla birlikte, şimdiye kadar terminal alkin sübstitüe ftalonitrillerden terminal alkiniltiyo sübstitüe ftalosiyaninlerin eldesiyle ilgili çok az sayıda çalışma bulunmaktadır ve bu tip ftalosiyaninler uç azid grubu taşıyan bileşiklerle klik kimyasında kullanılabilme potansiyeline sahip yapı taşlarıdır. Ftalosiyanin içeren polimerler fotodinamik terapiden koku gidermeye ve sitotoksik materyalden yakıt pillerine kadar çok çeşitli alanlarda uygulamalara sahiptir. Bununla birlikte hayal kırıklığına uğranmış olan çeşitli araştırma alanları da vardır. Konjuge polimerler son yılların yeni ilgi alanıdır fakat ftalosiyanin makro halkasının elektronik ve optik özelliklerinde avantaj sağlayan konjuge bir polimer örneği henüz elde edilememiştir. Konjuge ftalosiyanin içeren oligomerlerin literatürde yer almaya başlaması ümit vericidir. Bunun yanında katı fazda ftalosiyanin ünitesinin üç boyutlu düzenlenmesinde kovalent kontrolü sağlayan ftalosiyanin polimerlerin eldesi son zamanlarda başarılmıştır. Polimer içeren ftalosiyaninlerin senteziyle ve dizaynıyla ilgili hala çözülmesi gereken sorunlar bulunmaktadır. Şener ve arkadaşları, her bir benzo ünitesinde ester gruplarıyla birlikte terminal alkin grupları da içeren ftalosiyaninlerin sentezini gerçekleştirmiştir. Ayrıca klik kimyasını kullanarak bu ftalosiyanin bileşiğini türevlendirirken aynı zamanda metalli ftalosiyanine dönüşmesini de sağlamıştır. Torres ve grubu amfifilik olarak çevrelenmiş mono dispers çinko ftalosiyanin merkezli dendrimerlerin sentezini göstermiştir. İlgili ftalonitriller klik kimyası yaklaşımıyla elde edilen triazol motifiyle hazırlanmıştır. Nyokong ve çalışma arkadaşları Mn tetrakis(5-hekzinoksi) ftalosiyanin isimli yeni mangan kompleksini sahip olduğu alkin gruplarından dolayı klik reaksiyonuyla kontrollü sabitlenmiş elektrot üzerinde kullanmak amacıyla sentezlemiştir. Pc halkasına yerleştirilen terminal alkin grupları “klik” edilebilirliği sağlarken, sulfanil/tiyo/merkapto grupları da oluşan Pc’nin UV-Vis spektrumunda Q bandının yakın IR bölgesine kaymasına sebep olmakta ve böylece ftalosiyaninler fotosensör olarak kullanılabilmektedirler. 1992 yılında, Dolotova ve arkadaşları nonkoordine çözücülerde koordinasyon kimyasını incelemek üzere periferal olarak sübstitüe bir seri mangan ftalosiyanin sentezlemişlerdir. Bu amaçla 4-tert-butoksi-, tert-butiltiyo- ve 3-feniltiyo-ftalonitriller sentezlenmiş ve elde edilen MnPc’lerin kırmızı bölgeye kaydığı gözlenmiştir. Aynı grup son zamanlarda ilgili ftalonitrillerden nonperiferal ve periferal sübstitüe MnPc’leri koordinasyon ve elektrokimyasal incelemeler yapmak üzere sentezlemişlerdir. McGrath ve grubu sekiz adet alkin grubu taşıyan, yakın-IR bölgede absorbansa sahip, çözünür, Pc’ler sentezlemişlerdir. Pc’lerden birini çeşitli azid uç grubu taşıyan bileşiklerle alkin-azid klik kimyasında iskelet yapı olarak kullanmıştır. Böylece foto ve termal krosbağlanabilir, dendritik, hidrofilik grupları taşıyan ftalosiyaninlerden oluşan küçük bir ftalosiyanin kütphanesi tek bir Pc molekülünden başlayarak elde edilebilecektir. Alkin fonksiyonel grubunun Pc halkasına yerleştirilmesi alkin-azid klik kimyasını kolaylaştıracak ve birçok sübstitüentle fonksiyonlandırılmasına imkan sağlayacaktır. Terminal alkintiyo gruplarının Pc halkasına bağlanması az çalışılmış bir konudur. Bizim çalışmamızda, öncelikle 4-nitroftalonitril ile 3-propin-1-tiyol (propargil merkaptan) arasındaki nükleofilik yer değiştirme reaksiyonuyla terminal alkinil sübstitüe ftalonitril sentezi gerçekleştirilmiştir. Daha sonra, bu ftalonitril bileşiğinin siklotetramerizasyonuyla simetrik tetra terminal alkinil-sübstitüe ftalosiyaninler elde edilmiştir. Ayrıca, literatürdeki metoddan farklı olarak 4-nitroftalonitril ve 2-metil-2-propantiyol arasındaki reaksiyon ile 4-tertbutiltiyoftalonitril bileşiği elde edilmiştir. Daha sonra ilgili ftalonitril bileşiğinden simetrik tetra alkiltiyo-sübstitüe metalli ve metalsiz ftalosiyaninler de elde edilmiştir. Terminal alkin grupları taşıyan bu yeni ftalosiyaninler azid uç grubu taşıyan bileşiklerle klik kimyası ile fonksiyonlandırılabilme potansiyeline sahiptirler. Yeni tetra sübstitüe alkiltiyo grupları taşıyan ftalosiyaninler ise fotodinamik terapide kullanılabilme potansiyeline sahiptirler.
Phthalocyanines (Pcs) are two-dimensional 18 π-electron aromatic porphyrin synthetic analogues, consisting of four isoindole subunits linked together through nitrogen atoms. Recently they have attracted an increasing interest not only for the preparation of dyes and pigments but also as building blocks for the construction of new molecular materials for electronics and optoelectronics. Numerous properties arise from their electronic delocalization, which makes them valuable in different fields of science and technology. This is because that substituted Pc chromophores possess a number of unique physicochemical properties and improved organization capabilities, which render these compounds valuable applications in material science, in particular in photodynamic therapy and non-linear optics for optical limiting applications and optical signal detection techniques. The properties of phthalocyanines can be tuned by the introduction of substituents on the both periphery as well as non-periphery of the molecule. Due to π-stacking unsubstituted phthalocyanines are insoluble in common organic solvents which limits the processability, derivatisation and the characterization of this class of compounds. By introduction of bulky substituents at the ligand periphery intermolecular interaction of the π systems can be reduced, phthalocyanines become soluble. As a consequence, a variety of phthalodinitriles bearing alkyl, alkylthio and other functional groups have been synthesized and employed in cyclotetramerization reactions. During the last decade, a large number of mono- and poly-alkynyl-containing Pc-systems have been synthesized mainly following two different synthetic strategies consisting of the cyclotetramerization of alkynyl-substituted phthalonitriles and the incorporation of the alkynyl-containing moieties onto the preformed Pc macrocycle via some metal-catalyzed coupling reactions. However, terminal alkynyl substituted phthalonitriles have hitherto been rarely accessible for elaboration into terminalalkynylphthalocyanines that are potential building blocks for ‘click’ chemistry with any molecule bearing terminal azide group. Pc containing polymers have potential use in a wide range of applications and devices from photodynamic therapy to odour removal, and from cytotoxic materials to fuel cells. However, there are several areas of research where progress has been disappointing. Conjugated polymers have been the focus of renewed interest in recent years and yet there is still no bona fide example of a conjugate polymer which takes advantage of the unique electronic and optical properties of the Pc macrocycle. It is encouraging that reports of similar conjugated Pc containing oligomers have begun to appear in the literature. In addition, the promise of Pc polymers to enforce covalent control over the 3-dimensional arrangement of the Pc unit in the solid phase has yet to be fulfilled. Clearly, there are still exciting challenges to be met in the design and synthesis of Pc-containing polymers. Sener et. al. synthesized phthalocyanine derivatives carrying a terminal alkyne unit on each benzo group together with ester functionalities without protective/deprotective chemistry. Derivatization and in situ metallation of the alkynyl-substituted freebase Pcs was also accomplished using click chemistry. Torres et. al. showed the synthesis of monodisperse zinc phthalocyanine-centered dendrimers encapsulated within an amphiphilic environment. The corresponding phthalonitrile precursors have been prepared with a triazole linking motive as introduced through the “click” chemistry approach. Nyokong et. al. reported the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexynoxy) phthalocyanine, specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. While terminal alkyne moeity makes Pc macromolecule “clickable”, the sulphyanyl/thio/mercapto groups shifts the Q band to NIR region, which opens the door of photosensitization. In 1992, Dolotova et al. reported a number of peripherally substituted complexes for manganese Pcs, in order to study the coordination chemistry of the compounds in noncoordinating solvents. With this aim they synthesized 4-tert-butoxy-, tert-butylthio- and 3-phenylthio-phthalonitriles and they observed enhanced bathochromic shifts of novel MnPcs. And recently, the same group carried out synthesis for both peripheral and nonperipheral substituted manganese phthalocyanines from the corresponding phthalonitriles in order to observe their coordination and electrochemistry. McGrath and coworkers reported a series of near-IR-absorbing soluble Pcs with eight alkyne moieties as side chains of the chromophore. One of these Pcs used as a scaffold for functional group using alkyne–azide click chemistry with various azides. This led to a small library of Pcs with photo and thermal crosslinkable, dendritic, and hydrophilic moieties starting from a single Pc molecule. Incorporation of alkyne functionalities on the periphery of a Pc will facilitate alkyne-azide click chemistry, allowing for a variety of high-functioning substituents to be used. In line with mentioned statements, placing terminal alkynylthio groups on the periphery of phthalocyanines are rarely studied.. With this approach, firstly, we aimed the preparation terminal alkynylthio-substituted phthalonitrile using the nucleophilic displacement reaction between 4-nitrophthalonitrile and 3-propyne-1-thiol (propargyl mercaptan) . In addition to this, by different method 4-tert-butylthio-phthalonitrile is synthesized from 2-methyl-2-propanethiol and 4-nitrophthalonitrile. Then, symmetrically tetra-terminal alkynylthio and alkylthio substituted phthalocyanines are synthesized by cyclotetramerization of corresponding phthalonitrile precursors. This newly synthesized tetra-terminalalkynyl substituted phthalocyanines have potential for ‘click’ chemistry with any molecule bearing terminal azide group. In adddition, novel tetra alkylthio substituted phthalocyanines may have application in photodynamic therapy.
Phthalocyanines (Pcs) are two-dimensional 18 π-electron aromatic porphyrin synthetic analogues, consisting of four isoindole subunits linked together through nitrogen atoms. Recently they have attracted an increasing interest not only for the preparation of dyes and pigments but also as building blocks for the construction of new molecular materials for electronics and optoelectronics. Numerous properties arise from their electronic delocalization, which makes them valuable in different fields of science and technology. This is because that substituted Pc chromophores possess a number of unique physicochemical properties and improved organization capabilities, which render these compounds valuable applications in material science, in particular in photodynamic therapy and non-linear optics for optical limiting applications and optical signal detection techniques. The properties of phthalocyanines can be tuned by the introduction of substituents on the both periphery as well as non-periphery of the molecule. Due to π-stacking unsubstituted phthalocyanines are insoluble in common organic solvents which limits the processability, derivatisation and the characterization of this class of compounds. By introduction of bulky substituents at the ligand periphery intermolecular interaction of the π systems can be reduced, phthalocyanines become soluble. As a consequence, a variety of phthalodinitriles bearing alkyl, alkylthio and other functional groups have been synthesized and employed in cyclotetramerization reactions. During the last decade, a large number of mono- and poly-alkynyl-containing Pc-systems have been synthesized mainly following two different synthetic strategies consisting of the cyclotetramerization of alkynyl-substituted phthalonitriles and the incorporation of the alkynyl-containing moieties onto the preformed Pc macrocycle via some metal-catalyzed coupling reactions. However, terminal alkynyl substituted phthalonitriles have hitherto been rarely accessible for elaboration into terminalalkynylphthalocyanines that are potential building blocks for ‘click’ chemistry with any molecule bearing terminal azide group. Pc containing polymers have potential use in a wide range of applications and devices from photodynamic therapy to odour removal, and from cytotoxic materials to fuel cells. However, there are several areas of research where progress has been disappointing. Conjugated polymers have been the focus of renewed interest in recent years and yet there is still no bona fide example of a conjugate polymer which takes advantage of the unique electronic and optical properties of the Pc macrocycle. It is encouraging that reports of similar conjugated Pc containing oligomers have begun to appear in the literature. In addition, the promise of Pc polymers to enforce covalent control over the 3-dimensional arrangement of the Pc unit in the solid phase has yet to be fulfilled. Clearly, there are still exciting challenges to be met in the design and synthesis of Pc-containing polymers. Sener et. al. synthesized phthalocyanine derivatives carrying a terminal alkyne unit on each benzo group together with ester functionalities without protective/deprotective chemistry. Derivatization and in situ metallation of the alkynyl-substituted freebase Pcs was also accomplished using click chemistry. Torres et. al. showed the synthesis of monodisperse zinc phthalocyanine-centered dendrimers encapsulated within an amphiphilic environment. The corresponding phthalonitrile precursors have been prepared with a triazole linking motive as introduced through the “click” chemistry approach. Nyokong et. al. reported the synthesis of a new manganese phthalocyanine complex, namely Mn tetrakis(5-hexynoxy) phthalocyanine, specifically designed to possess an alkyne moiety for its potential use in controlled immobilization on electrodes via the so called “click” chemistry reaction. While terminal alkyne moeity makes Pc macromolecule “clickable”, the sulphyanyl/thio/mercapto groups shifts the Q band to NIR region, which opens the door of photosensitization. In 1992, Dolotova et al. reported a number of peripherally substituted complexes for manganese Pcs, in order to study the coordination chemistry of the compounds in noncoordinating solvents. With this aim they synthesized 4-tert-butoxy-, tert-butylthio- and 3-phenylthio-phthalonitriles and they observed enhanced bathochromic shifts of novel MnPcs. And recently, the same group carried out synthesis for both peripheral and nonperipheral substituted manganese phthalocyanines from the corresponding phthalonitriles in order to observe their coordination and electrochemistry. McGrath and coworkers reported a series of near-IR-absorbing soluble Pcs with eight alkyne moieties as side chains of the chromophore. One of these Pcs used as a scaffold for functional group using alkyne–azide click chemistry with various azides. This led to a small library of Pcs with photo and thermal crosslinkable, dendritic, and hydrophilic moieties starting from a single Pc molecule. Incorporation of alkyne functionalities on the periphery of a Pc will facilitate alkyne-azide click chemistry, allowing for a variety of high-functioning substituents to be used. In line with mentioned statements, placing terminal alkynylthio groups on the periphery of phthalocyanines are rarely studied.. With this approach, firstly, we aimed the preparation terminal alkynylthio-substituted phthalonitrile using the nucleophilic displacement reaction between 4-nitrophthalonitrile and 3-propyne-1-thiol (propargyl mercaptan) . In addition to this, by different method 4-tert-butylthio-phthalonitrile is synthesized from 2-methyl-2-propanethiol and 4-nitrophthalonitrile. Then, symmetrically tetra-terminal alkynylthio and alkylthio substituted phthalocyanines are synthesized by cyclotetramerization of corresponding phthalonitrile precursors. This newly synthesized tetra-terminalalkynyl substituted phthalocyanines have potential for ‘click’ chemistry with any molecule bearing terminal azide group. In adddition, novel tetra alkylthio substituted phthalocyanines may have application in photodynamic therapy.
Açıklama
Tez (Yüksek Lisans) -- İstanbul Teknik Üniversitesi, Fen Bilimleri Enstitüsü, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Thesis (M.Sc.) -- İstanbul Technical University, Institute of Science and Technology, 2013
Anahtar kelimeler
ftalosiyanin,
porfirin,
alkinil,
merkaptan,
klik kimyası,
phthalocyanines,
porphyrines,
alkynyl,
mercaptan,
click chemistry