Pirimidin türevi içeren yeni tür ftalosiyaninlerin sentezi ve karakterizasyonu
Synthesis and characterization of new types of phthalocyanines containing pyrimidine derivatives
Yazar: BİLGE YAZAR
Danışman: PROF. DR. MERYEM NİLÜFER YARAŞIR
Sakarya Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı / Anorganik Kimya Bilim Dalı
Derece: Yüksek Lisans, 2024
Konu: Kimya = Chemistry

Özet:
Ftalosiyaninler, 18 π elektronlu delokalize bir sistem içeren önemli aromatik yapılı makrosiklik bileşiklerdir. Bu bileşikler, benzersiz elektronik, optik ve yapısal özelliklere sahiptir ve tetrapirol halkasının bir parçası olarak, yüksek teknolojik uygulama potansiyali nedeniyle büyük ilgi çeker. Bu çalışmada, başlangıç maddesi 4-(4-aminopirimidin-2- iltiyo) ftalonitril (1) 2-tiyositozin/ 4-amino-2-tiyopirimidin ve 4-nitroftalonitrilin susuz K2CO3 içeren kuru DMF çözeltisinde oda sıcaklığında azot altında reaksiyona sokulması ile elde edilmiştir. Sentezlenen başlangıç maddesi 4-(4-aminopirimidin-2-iltiyo) ftalonitril (1) ile yeni tip pirimidin türevi içeren 2(3), 9(10), 16(17), 23(24)- tetrakis (4-aminopirimidin-2-iltiyo) bakır (II) ve kobalt (II) ftalosiyanin molekülleri (2,3) ve bu moleküllerin metillenmiş türevlerinin (2a,3a) sentezi gerçekleştirilmiştir. Başlangıç maddesi 4-(4-aminopirimidin-2-iltiyo) ftalonitril (1) 'in molekül yapısı tek bir kristal X-ışını kırınım (XRD) deneyi ile doğrulanmıştır. Deneyde 0,24×0,23×0,12 mm boyutlarında renksiz ve plaka tipi tek kristal numune kullanılmıştır. Daha sonra 4-(4-aminopirimidin-2-iltiyo) ftalonitril (1) maddesi kullanılarak periferal pozisyonlardan kükürt köprüleri ile bağlı tetra sübstitüye bakır ve kobalt içeren ftalosiyanin türevleri (2,3) ve bunların metillenmiş türevleri (2a,3a) sentezlenmiştir. Sentezlenen tüm bileşikler, sıcak ve soğuk organik/inorganik çözücülerle yıkama ve kolon kramotografisi gibi yöntemlerle saflaştırılmıştır. Elde edilen tüm bileşiklerin yapısı, elementel analiz UV-Vis, FT-IR, 1H-NMR, 13C-NMR ve MALDI-TOF MS kullanılarak doğrulanmıştır. Kuarternize işleminden sonra metillenmiş türevlerin (2a,3a) biyolojik uygulamalarda kullanılabilirliği için önemli olan su, organik çözücü DMF ve DMSO gibi çözücülerde iyi bir çözünürlüğe sahip olduğu gözlenmiştir. Ftalosiyaninlerin konsantrasyonları arttırıldığında, Lambert-Beer yasasına göre agregasyonun olmamasını desteklemiştir. Ancak, metillenmiş türevler (2a, 3a), su çözücüsünde bir H tipi agregasyon olduğunun bir göstergesi olan yeni bir bandın mavi dalga boyuna doğru kayması ftalosiyaninler için tipik absorpsiyon spektrumları olduğunu göstermektedir. Agregasyonun oluşması nedeniyle, bu mavi dalga boyuna kayan bantlar sırasıyla (2a) için 630 nm ve (3a) için 617 nm'de gözlenmiştir. Metillenmiş türevlerin (2a,3a) su çözeltilerine bir yüzey aktif maddesi olan (triton x-100) eklenmesinden sonra, kobalt metali içeren metaloftalosiyanin (2a) için herhangi bir değişiklik gözlenmemiştir. Bu mevcut agregasyonun triton x-100 ilavesiyle kırıldığını ve 668 (Q-bandı), 600 (n-π*) ve 336 (Soret-band)'da yeni bantların gözlemlenmesine uygun olarak (3a) için monomerik türlerin oluşumunu desteklemiştir.

Abstract:
The word "phthalocyanine" comes from the Greek words "cyanine," which means dark blue, and "naphtha," which means mineral oil. The synthesis of phthalocyanine happened by accident in 1907; Reginald P. Linstead was working at the Imperial College of Science and Technology when he coined the term to describe a new class of organic compounds .Phthalocyanines are mostly used in dye and pigment formulations. They are also used in many other applications, including chemical sensors, photoconductive materials in copying devices, electrocatalysis, electrochromism agents, photodynamic therapy, and in biological applications. Almost any metal ion can be used in place of two hydrogen atoms to create a variety of metal phthalocyanines. At the moment, approximately seventy different elements are used as the center atom in phthalocyanins. When substituents are added to peripheral positions, intermolecular distance rises and resolution improves. Metal-free phthalocyanines and metal phthalocyanines without peripheral substituents show low solubility in organic solvents, restricting their potential. Phthalocyanine characterization also makes use of standard organic compound characterization techniques like elemental analysis, IR, NMR, and UV-Vis. Since substituents and the central metal atom affect the Q-band's position in the visible zone, this technique is crucial for understanding phthalocyanine.
Beginning with the synthesis of a novel starting material, 4-(4-aminopyrimidin-2-ylthio) phthalonitrile (1), the molecular structure of this compound was confirmed by means of a single crystal X-ray diffraction (XRD) experiment. To summarize, the synthesis of 4-(4-aminopyrimidin-2-ylthio) phthalonitrile (1), as the initial compound, involved a reaction between 4-Amino-2-thiopyrimidine and 4-nitrophthalonitrile in dry DMF solvent containing anhydrous K2CO3 at room temperature under a nitrogen atmosphere for roughly two days. After a number of purification techniques, including column chromatography, the compound was crystallized in methanol-acetone (1/1 (v/v)) in order to remove impurities. The crystallization process allowed the compound to crystallize out of the solution. Then, In order to synthesise phthalocyanines (2,3), the starting material, "4-(4-aminopyrimidin-2-ylthio) phthalonitrile (1)," was combined with anhydrous metal salts (copper (II) chloride/cobalt (II) chloride) in dry (N,N-dimethylaminoethanol) DMAE solvent (2 mL) containing a catalytic amount of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The reaction was carried out at reflux temperature with stirring for eight hours. After that, a quaternization process was used to give phthalocyanines (2,3) water solubility. In order to synthesize the methylated derivatives (2a,3a), (dimethyl sulfate) DMS, a quaternizing agent, was used in DMF solvent at 120 °C.
The Q band and Soret band (B) are two prominent absorption peaks found in UV-Vis spectroscopy. When synthesized phthalocyanines (2,3) were analyzed in a DMSO solvent, the Q band absorptions were found at 684 nm and 670 nm, respectively, which
xxiv
is similar to typical metallophthalocyanines. Moreover, the Soret (B) band absorptions, which are indicative of phthalocyanine formation, were found at 347 nm and 334 nm for compounds (2) and (3) respectively.
The FT-IR spectra of 4-(4-aminopyrimidin-2-ylthio) phthalonitrile (1) showed that the -NH2 group had peaks at 3453 cm-1 (asymmetric N-H stretch), 3381 cm-1 (symmetric N-H stretch), and 3295 cm-1 (N-H bend overtone), in addition to strong peaks like NH2 scissors at 1635 cm-1 and out-of-plane bend at 721 cm-1. The CN stretching vibration at 2240 cm-1 vanished when starting material (1) was converted to phthalocyanine, confirming the formation of phthalocyanines (2,3). All obtained phthalocyanines showed similarities to the starting material (1), with the exception of minor shifts. The specific vibrations at 1321-1310 cm-1 (strong asymmetric stretching of S=O), 1205-1203 cm-1 (strong symmetric stretching of S=O), 744-742 cm-1 (C-S stretching), and 608-531 cm-1 (S-O stretching) that the methylated derivatives (2a,3a) displayed upon reaction with DMS indicated the quaternization of the corresponding phthalocyanines (2,3).
The proton signal from the –NH2 group was found at 7.16 ppm as a singlet in the 1H-NMR and 13C-NMR ([d6]-DMSO) spectra of the first compound (1). The carbon signals (ppm) of (1) were found at 167.70, 164.09, 155.88, 139.78, 138.67, 138.37, 134.58, 116.52, 116.21, 115.54, 114.10, and 103.61. The protonated ion peak of the starting material (1) was prominently seen at 253.935 [M]+.
The MALDI-TOF MS (Dithranol, m/z) analysis produced data consistent with the intended structures, validating the structures of all compounds studied in this study. The synthesized phthalocyanines (2,3) had protonated ion peaks of 1077.754 [M+H]+ and 1073.786 [M+H]+ respectively. The methylated derivatives (2a,3a) gave good results with peaks for potassium and sodium adducts, including 1132.863 [M-2SO4-4H]+, 1330.741 [M+2H]+, and 1129.328 [M-2SO4-3H]+ for (2a) and 1132.863 [M-2SO4-4H]+ for (3a).
The possible aggregation of phthalocyanines (2,3) in DMSO solvent at different concentrations was investigated in this work using dilution studies. As the concentration of phthalocyanine increased, the rise in Q band absorption that was seen along with the lack of any additional band formation in the spectrum supported the idea that there was no aggregation. This was the case in the concentration range of roughly 10.0 × 106- M to 6.25 × 107- M, which is in line with the Lambert-Beer law. The methylated derivatives (2a,3a) on the other hand showed characteristic absorption spectra suggestive of aggregated phthalocyanines in water, as demonstrated by the appearance of a new blue-shifted band at 630 nm for (2a) and 617 nm for (3a), respectively, indicating the presence of H-type aggregation (facial aggregation) in the aqueous solvent. The methylated derivatives (2a, 3a) were subjected to the addition of a surfactant (Triton X-100) to the water solutions. The results showed that the metallophthalocyanine (3a) with cobalt in the inner core inhibited the formation of aggregation, while the metallophthalocyanine (2a) with copper in the inner core did not exhibit any change. This suggests that the aggregation that was already present was broken up by the addition of Triton X-100, resulting in the formation of monomeric species for (3a), which is consistent with the observation of new bands at 668 (Q-band), 600 (n-π*), and 336 (Soret-band).
Aggregation, one of the most strinking properties of phthalocyanines, occurs when the two or more extended π-system of phtlocyanines are top of eac other or side by side due to intermoleculer attraction forces. These clusters, which are formed by or atoms coming together as a result of these interactions, depending on the metal atom placed in the inner core, the natüre and concentration of the substituents, the solvent used and the temperature, are called aggregates. İn the study, whether phthalocyanines (2,3) aggregaqted at different concentrations was investigated by dilution studies in DMSO solvent. However, phthalocyanines with methylated structured derivatives (2a,3a) gave typical drop ranges for phthalocyanines collected in water, observing a new blue slip group that appears in ten as a result of H-type aggregation in aqueous solvents.