Tetrapirazinoporfirazinin yaygın olarak kullanılan diğer isimlendirilmesi ‘azaftalosiyanin’dir. Bu çalışmada, periferalde heteroatom olarak S-sübstitüe simetrik metalli ve metalsiz azaftalosiyaninler ve suda çözünür katyonik türevleri sentezlenmiştir. Metalli AzaPc’ler ftalosiyaninler gibi sentezlenen ligandtan doğrudan uygun metal tuzları mevcudiyetinde siklomerizasyonla ya da porfirazinler gibi metalsiz türeve metal girmesiyle kolaylıkla hazırlanabilir. Metalsiz AzaPc’ler dilityum veya magnezyum AzaPc’den zayıf veya kuvvetli asit kullanılarak elde edilebilir. Başlangıç maddesi olarak 5,6-dikloropirazin-2,3-dikarbonitril 1 seçilmiştir ve diaminomaleodinitrilden (DAMN) iki adım reaksiyon ile kolaylıkla hazırlanmıştır. Elde edilen 5,6-dikloropirazin-2,3-dikarbonitril 1, pirazin-2,3-dikarbonitril kısmı ve klorür atomlarının güçlü elektron çekme özelliğinden dolayı 5 ve 6 pozisyonundan nükleofillerle kolay sübstitüsyona uğrar. Hedeflenen ligandı sentezlemek için, 1 bileşiği 2-dimetilaminoetantiyol hidroklorür ile oda sıcaklığında muamele edilmiştir. Azaftalosiyanin 3, magnezyum propanolat varlığında yüksek verimde sentezlenen 2 bileşiğinin tipik siklotetramerizasyon reaksiyonu ile hazırlanmıştır. Metalsiz AzaPc 4, magnezyum AzaPc 3’ün trifloroasetik asit ile muamelesiyle hazırlanmıştır. Çinko AzaPc 5’in sentezi, metalsiz AzaPc 4’ün, çinko (II) asetat ile reaksiyonundan elde edilirken, kobalt AzaPc 6 ftalosiyaninlerdeki olduğu gibi 5,6-bis(2-dimetilaminoetilsülfanil)-2,3-disiyanopirazin 2 bileşiğinin direkt kobalt (II) asetat ile reaksiyonundan sentezlenmiştir. Bu azaftalosiyaninler suda çözünür kuaternize ürünlere metil iyodür ile reaksiyon sonucu dönüştürülmüştür. Agregasyon olayı, belirli bir pH aralığında dimetilamino sübstitüe magnezyum azaftalosiyanin için incelenmiştir. Elde edilen bu bileşikler FT-IR, 1H NMR, kütle ve UV-Vis spektral değerleriyle karakterize edilmiştir. Anahtar Kelimeler: Azaftalosiyanin, agregasyon, pirazin.Tetrapyrazinoporphyrazines (TPyPzs) are the structures that are formed from the annulation of four pyrazine rings to the porphyrazine (Pz) framework. Other extensively denomination use of TPyPz is "azaphthalocyanine"(AzaPc). In comparison to phthalocyanines (Pcs), the eight additional nitrogen atoms in TPyPzs induce large electronic effects on the structure. AzaPcs are formed by cyclotetramerisation of pyrazine-2,3-dicarbonitrile or its substituted derivatives. Like Pcs, AzaPcs can be substituted in their peripheral 2,3-positions. This situation may further enhance their solubility of substituted TPyPzs and their metal complexes in organic solvents and also influence the electronic excitation energies of these compounds. The TPyPzs have specific optical properties because they have symmetrical rich 18 p-electron aromatic macrocycle, which can play host to different metal ions in its central cavity. Therefore, they have been extensively used in optical recording media, photosensors, optical filters and copy preventing inks. In this work, octasubstituted symmetric metallo and metal-free azapcs containing sulphur as heteroatom on the periphery and their cationic derivatives that are soluble in water were synthesized. Metallo azapcs can be readily prepared either by a direct cyclotetramerisation of dinitrile precursors like Pcs or by a metal insertion into metal-free derivative as Pzs in the presence of corresponding metal salts. Metal-free azapcs can be obtained from either dilithium or magnesium azapc using weak or strong acid. For this porpuse, 5,6-dichloropyrazine-2,3-dicarbonitrile 1, that is easily accessible from diaminomaleodinitrile (DAMN) in a two step reaction, was chosen as a starting material. Because of the strong electron withdrawing ability of cyano and chlorine atoms, this compound undergoes ready substitution in positions 5 ve 6 with nucleophiles like primary and secondary amines, alcoholates, thiolates. Consequently, treating 1 with 2-dimethylaminoethanthiol hydrochloride at room temperature afforded 2 in rather high yield. In order to convert to ligand 2 into azapc 3, we made use of its template reaction in the presence of magnesium propanolate. Mg azapc 3 was crystallized from ethanol/water. Treatment of Mg azapc 3 with trifluoroacetic acid gave the metal-free azapc 4. Zinc azapc 5 was prepared through the insertion of Zn ion into metal-free azapc 4. However, the cobalt azapc 6, was directly synthesized by cyclotetramerization of 2 in the presence of anhydrous cobalt acetate. When azapcs 3 and 4 were treated with methyliodide in chloroform, the hygroscopic azapc products 7 and 8 with eight quaternary ammonium groups were obtained. The new compounds were characterized by using standard spectral methods (elemental analysis, 1H NMR, UV/Vis, IR and Mass spectroscopy). From the FT-IR spectrum of 2 , the characteristic stretching vibrations of CºN group was observed at 2232 cm-1. When the precursor 2 was converted into new metallo or metal-free azapcs (3, 4, 5, 6), this sharp peak disappeared as a proof of the cyclotetramerization reaction of dinitrile. IR spectra of azapcs 3, 5 and 6 is similar to the IR spectrum of dinitril compound 2. In the IR spectrum of 4 the NH groups in the inner core give absorption at 3292 cm-1. Besides, no major change in the IR spectra was found after quaternization. In the 1H NMR spectrum of compound 2 (CDCl3), the aliphatic protons are observed at 3.38(S-CH2), 2.63(N-CH2) and 2.30 (CH3) ppm. 1H NMR spectra of 3 and 4 are almost the same as compound 2. However, 1H NMR spectrum of metal-free azapc 4 shows an additional peak at -3.32 ppm due to NH groups in the inner core. Furthermore, in the mass spectrum, we observed the molecular ion peaks at m/z: 337.10 for 2 and at m/z: 1410.7 for 5 which confirm the proposed structures. In the electronic absorption spectra of the complexes (3, 5 and 6), Q bands were observed at 644, 644 and 648 nm, respectively in CHCl3. The D2h symmetry of the metal-free azapc 4 is verified by two broad absorptions in the visible region (633-658 nm). A second intense and broad p-p* transition in the range 358-373 nm which is called Soret or B band is also a characteristic band as expected for tetrapyrroles. When the UV-Vis spectra of quaternized products 7 and 8 were analyzed in aqueous solution. Besides, in this study aggregation properties that can be observed at UV-vis spectrum of Mg azapc 3 were investigated by the dropwise addition of 0.01 M HCl to their THF solution. Keywords: Azaphthalocyanine, aggregation, pyrazine
