Yeni tip ftalosiyanin boyar maddelerinin sentezi ve karakterizasyonu
Synthesis and characterization of new types of phthalocyanine dyes
- Tez No: 929541
- Danışmanlar: PROF. DR. MERYEM NİLÜFER YARAŞIR
- Tez Türü: Yüksek Lisans
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 2025
- Dil: Türkçe
- Üniversite: Sakarya Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Anorganik Kimya Bilim Dalı
- Sayfa Sayısı: 83
Özet
Porfirin anologlarından olan ftalosiyaninler, birden fazla izoindol biriminden oluşan ve 18 π elektronu taşıyan geniş bir halkaya sahip yapılar olarak tanımlanır. Ftalosiyanin terimi, Yunanca“koyu mavi”ve“mineral yağ”kelimelerinden türetilmiştir. Bu makrosiklik bileşiklerdeki elektronların serbest hareketi, onlara benzersiz optik ve elektriksel özellikler kazandırır. Ftalosiyaninler, boya, polimer teknolojisi, tıp, ve ilaç endüstrisi gibi çeşitli uygulama alanına sahiptirler. Özellikle çözünürlük sorunları aşıldığında daha da yaygın bir şekilde kullanılabilirler. Metal içeren ftalosiyaninler, çeşitli metal iyonları ile sentezlenebilir ve halka pozisyonlarına farklı fonksiyonel gruplar eklenerek çözünürlükleri artırılabilir. Metal içermeyen ve periferal pozisyonda sübstitüent bulunmayan ftalosiyaninler ise organik çözücülerde düşük çözünürlük göstererek değişik yerlerde uygulama potansiyellerini sınırlamaktadır. Bu nedenle, bu moleküllerin çözünürlüklerinin arttırılması ve uygulama alanlarının genişletilmesi önemlidir. Ftalosiyaninler arasındaki güçlü moleküler etkileşimler, agregasyonlara yol açarak çözünürlüklerini düşürebilir. Ftalosiyaninlerin özelliklerini belirlemek için IR, UV-Vis ve NMR gibi standart analiz teknikleri kullanılır. Bu yöntemler, sübstitüentlerin ve merkezi metal atomunun Q-bandının görünür bölgedeki konumunun tespit edilmesinde önem taşır. Bu çalışmada, sübstitüsyona uğramamış ftalosiyanin bileşiklerine kıyasla daha uzun absorpsiyon dalga boylarına sahip yeni tip ftalosiyanin molekülü olarak çinko, bakır ve kobalt (2,3,4) ftalosiyaninler sentezlenmiştir. Sentezde başlangıç maddesi olarak 3-(3-kloro-4-florofenoksi) ftalonitril (1) bileşi kullanılmış ve elde edilen bileşiğin yapısal doğruluğunu teyit etmek amacıyla mono kristal X-ışını kırınımı (XRD) analizi uygulanmıştır. Sentez süreci, 3-(3-kloro-4-florofenoksi) ftalonitrilin (1) uygun reaksiyon koşulları altında reaksiyona girmesiyle başlamakta olup, ardından elde edilen bileşikler çeşitli analiz teknikleriyle karakterize edilmiştir. UV-Vis spektroskopisi, ftalosiyanin bileşiklerinin optik özelliklerini belirlemek için önemli bir araç olmuştur. FT-IR spektrumları, bileşiklerin yapısal analizini yapmak amacıyla incelendi. 1H-NMR ve 13C-NMR spektroskopisi, moleküler yapıların daha ayrıntılı bir şekilde araştırılmasını sağlamıştır. Ayrıca, MALDI-TOF MS analizi, sentezlenen bileşiklerin doğruluğunu teyit için gerçekleştirilmiştir. Sonuç olarak, bu çalışma yeni tip ftalosiyanin moleküllerinin sentezi ve karakterizasyonuna odaklanmıştır. Sentezlenen bileşiklerin yapıları, çeşitli analiz teknikleriyle doğrulanmış ve karakterize edilmiştir. Bu çalışma, ftalosiyaninlerin potansiyel uygulama alanlarını daha iyi anlamamıza katkı sağlamıştır. Ele geçen bulgular, ftalosiyanin bileşiklerinin sentezi ve karakterizasyonu konusundaki literatüre yeni bir pencere açmış olup, bu bileşiklerin endüstriyel alandaki potansiyel kullanımını daha kapsamlı bir şekilde keşfetmemize olanak tanıyacaktır.
Özet (Çeviri)
Compounds containing cyclic structures and heteroatoms are defined as macrocyclic compounds in chemical terminology. Organic ligands can form complexes with metal ions by creating such large cyclic structures. Studies have revealed that organic ligand complexes containing macrocyclic groups exhibit significantly different properties compared to compounds that lack such groups. In 1907, phthalocyanine was accidentally synthesized by Reginald P. Linstead at Imperial College London, where he coined the term to identify a new class of organic compounds. The term“phthalocyanine”comes from the Greek words“cyanine,”which means dark blue, and“naphtha,”referring to mineral oil. After the discovery of phthalocyanine compounds in the early 20th century, their structures were further detailed through research conducted in 1934. Since then, they have played a significant role in the dye industry due to their superior pigment properties in shades of blue and green. In recent years, phthalocyanine complexes have gained significant interest because of their exceptional technological properties. Their versatility allows for modifications to optimize performance in various applications. Recent studies have focused on uncovering the fundamental mechanisms behind the unique characteristics of these compounds. Phthalocyanines are widely used in diverse fields, including dye and polymer technology, pharmaceuticals, medicine, biological process analysis, agriculture, etc. As a result, the number of studies on phthalocyanine complexes continues to grow. As an example of these studies, between 1929 and 1933, Linstead and his team elucidated the structure of phthalocyanine molecules through detailed experiments. Linstead verified the accuracy of these structures using various physicochemical measurements and demonstrated that phthalocyanines possess a planar geometry by employing X-ray and electron microscopy techniques. The first metal-containing phthalocyanine compound was obtained by researchers Van der Weid and Diesbach. They heated copper cyanide with o-dibromobenzene in pyridine at 200°C, yielding insoluble copper phthalocyanine; however, they were unable to elucidate its structure. However, solubility remains one of the critical challenges for their application in high-tech industries. To solve this issue, soluble phthalocyanine complexes with advanced properties must be synthesized. Phthalocyanines are compounds known for their chemical and thermal stability, as well as their resistance to strong acids and high temperatures. These properties make them highly valuable for industrial applications. However, challenges encountered during purification processes are particularly evident in unsubstituted phthalocyanine types. With traditional purification methods, unsubstituted phthalocyanines can generally be purified by dissolving them using sublimation techniques or concentratedsulfuric acid, followed by precipitation in ice-cold water. These methods can work effectively based on the physical properties of phthalocyanines, as these compounds generally remain stable in high-temperature and acidic environments. This technique is commonly used to obtain pure phthalocyanines. However, classical purification methods are generally not applicable to phthalocyanines that contain substituents. These types of phthalocyanines may exhibit different chemical and physical properties due to the presence of substituents. In particular, some phthalocyanines may decompose when interacting with purified sulfuric acid, altering their structure in this environment. Other phthalocyanines may sulfonate the benzene rings or exhibit changes in solubility behavior. The presence of substituents can also affect their solubility properties, leading to challenges related to solubility. Therefore, common purification techniques like chromatography and crystallization are generally not suitable and are not preferred for these compounds. The inadequacy of these purification methods stems from solubility issues associated with phthalocyanines. Specifically, in cases requiring high solubility, these techniques have proven ineffective. For soluble phthalocyanines, crystallization and extraction methods can be employed. Crystallization is a commonly used technique for purifying dissolved phthalocyanines. In this process, unwanted compounds in the liquid phase are removed, and pure phthalocyanine is obtained in solid form. Extraction, on the other hand, is used to separate compounds with differing solubility. By using solvents, phthalocyanines can be extracted to the desired purity level. These methods are effective for purifying soluble phthalocyanines and generally provide more efficient results. In conclusion, the purification of phthalocyanines can vary depending on the techniques used and the structure of the compound. The presence of substituents affects the solubility properties of these compounds, making the purification process more complex. Therefore, special methods such as crystallization and extraction are preferred for purifying soluble phthalocyanines. Metal ions replace two hydrogen atoms, leading to the formation of various metal phthalocyanines. Approximately seventy elements are employed as the central atom in phthalocyanines. Adding substituents to peripheral positions increases the intermolecular distance and improves solubility. Phthalocyanines without metal ions or peripheral substituents typically have limited solubility in organic solvents, which restricts their potential applications. The strong intermolecular π-π interactions between phthalocyanine molecules can lead to aggregation, decreasing their solubility. Phthalocyanine characterization is carried out using analytical methods. The location of the Q-band is influenced by the substituents and the central metal atom, which is important for understanding phthalocyanines. In this analysis, we have successfully synthesized new zinc (II) (2), copper (II) (3), and cobalt (II) (4) phthalocyanines, incorporating 3-chloro-4-fluorophenoxy groups. These modified compounds show longer absorption wavelengths in the UV-visible spectrum compared to the unsubstituted phthalocyanine compound. The synthesis of a novel precursor, 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1), began with a carefully controlled reaction. The molecular structure of this compound was validated using single-crystal X-ray diffraction (XRD) analysis. The synthesis process involved a reaction over approximately three days between 3-chloro-4-fluorophenol and 3-nitrophthalonitrile in dry DMF solvent under a nitrogen atmosphere, catalyzed by anhydrous K2CO3. Thin layer chromatography (TLC) was xxv used to periodically track the reaction's progress, confirming its completion and ensuring the desired product was formed. After the reaction was finished, it was terminated by slowly adding the mixture to about 300 mL of ice water mixture. The formed precipitate was collected through filtration and washed extensively with water until the filtrate reached a neutral pH, ensuring that any residual impurities were removed. The unrefined product was then further purified through column chromatography with a CHCl3-MeOH eluent (10:2 ratio by volume) to achieve effective separation based on polarity. Finally, the purified product was crystallized using a CHCl3-acetone solvent system (in a 5:1 volume ratio), yielding the desired product (1) as white, transparent crystals. To synthesize phthalocyanines (2, 3, 4), the precursor, 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1), was reacted with anhydrous metal salts (zinc (II) chloride, copper (II) chloride, and cobalt (II) chloride) in dry DMAE (N,N-dimethylaminoethanol) solvent (2 mL), with DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as a catalyst. The reaction was performed under reflux with continuous stirring for a duration of ten hours. UV-Vis spectroscopy is of critical importance in the comprehensive analysis of phthalocyanine compounds, offering valuable insights into their molecular structures and electronic characteristics. The distinct absorption peaks in the UV-Vis spectra provide important information regarding the nature of chemical bonds and atomic arrangements within these compounds. The Q band, typically found between 600-800 nm, is of particular significance as it reflects electronic transitions involving the molecular orbitals of the phthalocyanine system. Similarly, the Soret band (B), located between 300-400 nm, represents electronic transitions between the central metal ion and the surrounding ligands, shedding light on the compounds complex behavior. The synthesized phthalocyanines (2, 3, 4) were analyzed in THF solvent, showing absorptions in the Q band at 687, 688, and 673 nm, in order, in line with the typical values found in metallophthalocyanines. Additionally, the Soret (B) band absorptions, which are distinctive of the phthalocyanine structure, were detected at 346 nm, 341 nm, and 324 nm for compounds (2), (3), and (4), respectively. When the FTIR spectrum was examined, it was determined that the characteristic aromatic C–H stretching vibrations of 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1) appeared at 3069 cm⁻¹, while the sharp C≡N vibrations were observed at 2227 cm⁻¹. The asymmetric stretching vibrations of the Ar–O–Ar bond were observed around 1280 cm⁻¹, while the symmetric stretching vibrations were detected at approximately 1058 cm⁻¹. The C–F stretching vibrations were identified with remarkable intensity in the 1000–1300 cm⁻¹ range. Additionally, C–Cl stretching vibrations typically occur in the 600–800 cm-1 range in chlorinated benzene derivatives. In line with this, the C–F and C–Cl stretching vibrations of 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1) were prominently observed at 1252 cm-1 and 803 cm-1, respectively, in the FTIR spectrum. The FTIR spectra of compounds (2), (3), and (4) show significant similarity to that of the ligand compound (1), with only minor shifts in the absorption peaks. In particular, as a result of the cyclotetramerization reaction, the vibration corresponding to the sharp –CN groups of 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1) at 2227 cm⁻¹ disappeared, which is an important finding supporting the formation of (2), (3), and (4). In the 1H-NMR and 13C-NMR spectra of 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1) recorded in [d6]-DMSO, the aromatic proton signals appeared xxvi between 7.92 and 7.20 ppm. These signals were assigned as follows: 2H multiplet for the ortho and meta positions to –CN, 1H doublet of doublets for the ortho position to –F, 1H doublet of doublets for the ortho position to –Cl, and 2H multiplet for the para position to –CN and the meta position to –F. The carbon signals for 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1) were observed at the following ppm values: 160.173, 151.051, 136.802, 129.262, 123.218, 122.840, 121.653, 121.550, 119.156, 118.850, 116.556, 116.281, 113.978, and 105.972. The MALDI-TOF MS analysis, conducted with Dithranol as the matrix and using the m/z scale, provided results that confirmed who coined the term to define a novel group of organic compounds. Specifically, for 3-(3-chloro-4-fluorophenoxy) phthalonitrile (1), the protonated ion peak was observed at m/z 273.303 [M+H]+ with high density, which corresponds to the expected molecular weight of the compound, thereby confirming its structure (1). The prepared phthalocyanines (2,3 and 4) had protonated ion peaks of 1156.315 [M]+, 1154.256 [M]+ and 1150.202 [M+H]+ respectively.
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