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Alfa sübstitüe kükürt köprülü pirazin türevi içeren yeni tip ftalosiyaninlerin sentezi ve karakterizasyonu

Synthesis and characterization of new types of alpha-substituted phthalocyanines containing sulfur-bridged pyrazine derivatives

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  1. Tez No: 1017054
  2. Yazar: UMUT BURAK CANIBEK
  3. Danışmanlar: PROF. DR. ARMAĞAN GÜNSEL
  4. Tez Türü: Yüksek Lisans
  5. Konular: Kimya, Chemistry
  6. Anahtar Kelimeler: Ftalosiyaninler, Karakterizasyon, Pirazin, Sentez, Phthalocyanines, Characterization, Pyrazine, Synthesis
  7. Yıl: 2026
  8. Dil: Türkçe
  9. Üniversite: Sakarya Üniversitesi
  10. Enstitü: Fen Bilimleri Enstitüsü
  11. Ana Bilim Dalı: Kimya Ana Bilim Dalı
  12. Bilim Dalı: Anorganik Kimya Bilim Dalı
  13. Sayfa Sayısı: Belirtilmemiş.

Özet

Ftalosiyaninler, 18-π elektronlu delokalize sistemleri sayesinde üstün kimyasal, termal ve optik kararlılık sergileyen makrosiklik bileşikler sınıfında yer almaktadır. Merkezi boşluklarına periyodik tablodaki pek çok metali koordine edebilmeleri ve halka üzerindeki konumların fonksiyonel gruplarla modifiye edilebilmesi, bu yapıların teknolojik ve biyomedikal alanlarda stratejik bir konuma ulaşmasını sağlamıştır. Özellikle suda çözünürlük kazandırılmış türevleri, kanser tedavisinde kullanılan fotodinamik terapi (PDT) uygulamalarında yüksek verimli fotosensitizör adayları olarak değerlendirilmektedir. Bu yapısal esneklik, makrosiklik halkanın periferik veya periferik olmayan (alfa) mevkilerine yapılan sübstitüsyonlar aracılığıyla kontrol edilebilmektedir. Bu tez çalışması kapsamında, non-periferal pozisyonlarından kükürt köprüleri ile bağlı pirazin türevleri içeren yeni tip alfa tetra-sübstitüe ftalosiyaninlerin tasarımı, sentezi ve karakterizasyonu gerçekleştirilmiştir. Araştırmanın ilk aşamasında, başlangıç maddesi olarak 3-(2-(pirazin-2-il) etiltiyo) ftalonitril (1) bileşiği, 3-nitroftalonitril ile 2-(pirazin-2-il) etanetiyol'ün nükleofilik yer değiştirme reaksiyonu yardımı ile yüksek verimle elde edilmiştir. Sentezlenen bu yeni tip ftalonitril türevi başlangıç maddesi (1) yardımıyla, indiyum metal atomu içeren non-periferal tetra-sübstitüe ftalosiyanin türevi (2), 1-pentanol çözücüsü ve DBU bazı eşliğinde 160 °C'de 24 saat süreyle karıştırılarak gerçekleştirilen siklotetramerizasyon reaksiyonu ile sentezlenmiştir. Çalışmanın devamında, sentezlenen indiyum metal atomu içeren ftalosiyanin türevi (2), biyolojik ortamlardaki çözünürlüğü ve biyoerişilebilirliğini artırmak amacıyla DMF ortamında dimetil sülfat ile 120 °C'de 12 saat karıştırılarak kuaternerleştirme reaksiyonuna tabi tutulmuştur. Böylece, suda çözünebilen katyonik karakterli türev (2a) başarıyla elde edilmiştir. Elde edilen tüm yeni bileşiklerin moleküler yapıları; FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis ve MALDI-TOF kütle spektrometrisi gibi ileri düzey spektroskopik teknikler kullanılarak kapsamlı ve detaylı bir biçimde aydınlatılmıştır. Ayrıca, sentezlenen ftalosiyanin türevlerinin çözelti ortamındaki davranışları, UV-Vis spektroskopisi yardımıyla farklı solvent sistemleri içerisinde sistematik olarak incelenmiştir. Gerçekleştirilen spektral analizler sonucunda, bu bileşiklerin DMSO ortamında ağırlıklı olarak monomerik yapıda bulunduğu ve Beer-Lambert yasasına yüksek derecede uygunluk gösterdiği açıkça doğrulanmıştır. Buna karşılık, kuaternize türevin (2a) saf su ortamında moleküller arası etkileşimlerin etkisiyle H-tipi agregasyon (kümelenme) eğilimi sergilediği gözlemlenmiştir. Ancak, ortama triton X-100 gibi uygun bir yüzey aktif maddenin ilave edilmesiyle söz konusu agregasyonun önemli ölçüde azaldığı ve bileşiğin yeniden monomerik davranış sergilemeye başladığı tespit edilmiştir.

Özet (Çeviri)

Phthalocyanines belong to a class of macrocyclic compounds that exhibit exceptional chemical, thermal, and optical stability due to their 18-π electron delocalized systems. Their ability to coordinate a wide variety of metals within their central cavity, along with the possibility of functionalizing the ring positions with different substituents, has enabled these structures to attain a strategic role in technological and biomedical fields. In particular, water-soluble derivatives are considered highly efficient photosensitizer candidates for photodynamic therapy (PDT) in cancer treatment. This structural versatility can be controlled through substitutions at the peripheral or non-peripheral (alpha) positions of the macrocyclic ring. In this thesis, the novel“3-(2-(pyrazin-2-yl)ethylthio)phthalonitrile (1)”as starting material was synthesized and its non-peripherally tetra-“pyrazine derivative”-substituted phthalocynine compound (2) was synthesized for the first time. Then, its water soluble-quaternized phthalocyanine compound (2a) was prepared. A variety of spectroscopic techniques-including FT-IR, ¹H-NMR, ¹³C-NMR, and MALDI-TOF MS-were employed to confirm the successful synthesis of the target compounds. Compound (1) was synthesized via a nucleophilic substitution reaction between 3-nitrophthalonitrile and 2-(pyrazin-2-yl) ethanethiol under anhydrous conditions, using potassium carbonate (K2CO3) as a base in DMSO. The phthalocyanine macrocycle (2) was subsequently obtained through the cyclotetramerization of compound (1) in 1-pentanol, employing DBU as a catalyst and indium (III) chloride (InCl3) as the metal source, all performed under a nitrogen atmosphere to ensure an inert environment. To enhance the water solubility of phthalocyanine (2), a quaternization step was carried out by reacting it with dimethyl sulfate (DMS) in DMF at 120 °C, yielding the quaternized derivative (2a). The resulting compound displayed excellent solubility in water as well as in polar organic solvents such as DMSO and DMF. The FT-IR spectrum of compound (1) revealed key structural characteristics, notably a sharp absorption at 2236 cm-1 attributed to the -C≡N stretching mode, confirming the presence of nitrile groups. Additionally, bands typical of aromatic C-H stretching were detected in the range of 3081-3040 cm-1, while aliphatic C-H vibrations-both asymmetric and symmetric-were observed between 2965 and 2848 cm-1. In contrast, compounds (2) and (2a) exhibited no signal corresponding to the -C≡N stretch, supporting the successful transformation of the phthalonitrile precursor into phthalocyanine frameworks. The FT-IR spectra of these compounds also showed aromatic C-H stretching absorptions between 3061 and 3021 cm-1, as well as aliphatic C-H bands in the 2946-2853 cm-1 region. Following quaternization with DMS, compound (2a) displayed new FT-IR features characteristic of sulphate functionality: a strong asymmetric S=O stretch at 1326 cm-1, a symmetric S=O vibration at 1047 cm-1, C-S bond vibrations around 742 cm-1, and an S-O stretch near 575 cm-1. These findings are in agreement with established spectral data and confirm the successful modification of phthalocyanine (2) into its quaternized form (2a). In the ¹H-NMR spectrum of compound (1), signals attributed to aromatic protons appeared between 8.58 and 7.80 ppm, consistent with the presence of an aromatic ring system. Meanwhile, peaks observed in the 3.62 to 3.17 ppm range were assigned to aliphatic hydrogen environments. Complementary ¹³C-NMR analysis supported the structural assignment, providing further validation of the compound's carbon framework. MALDI-TOF mass spectrometry provided clear molecular evidence for the synthesized compounds. For compound (1), a major ion peak was observed at m/z 266,576, corresponding to the molecular ion [M]+ and confirming its expected molecular mass. Compound (2) produced a protonated molecular ion [M+H]+ at m/z 1216,435, while compound (2a) yielded a prominent signal at m/z 1720,171, matching the mass of its neutral molecular ion [M]+. These spectral findings are consistent with the proposed molecular formulas of the respective compounds. UV-Vis spectroscopy remains a vital technique for probing the electronic structure of phthalocyanines, which are known for their characteristic absorption features: the intense Soret (B) band typically appearing between 300-400 nm and the lower-energy Q band generally found in the 650-800 nm region. In this study, UV-Vis spectra of non-peripherally tetra-substituted phthalocyanines (2) and (2a) were recorded in DMSO and aqueous environments. In DMSO, compound (2) exhibited Q-band absorptions at 723 and 692 nm, along with B-band peaks at 342 and 348 nm. Upon quaternization, compound (2a) showed a noticeable blue shift of approximately 31 nm in its Q-band position, which can be attributed to the reduced electron-donating capability of the nitrogen atoms after their conversion into quaternary centers. Compound (2a) displayed well-defined monomeric absorption profiles in DMSO without the need for surfactants, whereas compound (2) demonstrated slight aggregation under similar conditions. However, the addition of a trace amount of Triton X-100 effectively disrupted these aggregates in (2), resulting in spectra consistent with monomeric forms. In aqueous media, (2a) exhibited aggregation behavior, evidenced by a blue-shifted absorption band characteristic of H-type (face-to-face) stacking interactions, commonly observed in phthalocyanine aggregates. Introduction of the nonionic surfactant Triton X-100 to the aqueous solution of (2a) led to the disappearance of the 681 nm band, signaling disaggregation. This was accompanied by the emergence of new absorption features at 686 nm (Q-band), 650 nm (n–π* transition), and 345 nm (Soret band), indicating a shift toward monomeric species. Such aggregation in metallophthalocyanines (MPcs) is typically driven by π-π stacking of their planar macrocyclic structures, resulting in broadened and blue-shifted spectral features. Although the presence of bulky 2-(pyrazin-2-yl) ethylthio substituents at the molecule's periphery improves solubility to some extent, it does not fully prevent intermolecular aggregation. In contrast, incorporating metal centers like indium-especially when paired with axial ligands and voluminous side chains-has proven more effective at reducing aggregation tendencies within phthalocyanine systems. In DMSO, compounds (2) and (2a) displayed sharp, well-defined Q-band absorptions in their UV-Vis spectra-indicative of monomeric species with minimal or no aggregation. To assess their aggregation tendencies more thoroughly, concentration-dependent spectral studies were conducted. As the concentration increased, the Q-band intensity rose proportionally, and no additional bands-often associated with aggregated states-were detected. This linear relationship suggests that both compounds remain molecularly dispersed in DMSO and follow the Beer-Lambert law across the tested concentration range (1.0 × 106- to 1.2 × 105- M). A comparable behavior was noted for compound (2a) in aqueous solutions containing Triton X-100, where the absorbance increased consistently with concentration within the same range, further supporting the stability of the monomeric form under these conditions.

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