Synthesis of porphyrazines containing 9-anthracenecarboxy esters at peripheral positions

SYNTHESIS OF PORPHYRAZ NES CONTAINING 9-ANTHRACENECARBOXYESTERS AT PERIPHERAL POZITIONSÖzgür ÖDEVCChemistry, Thesis, Master of ScienceThe two basic frames in tetrapyrrolic macrocyclic ring systems are porphyrins andtetraazaporphyrins, which include phthalocyanines and porphyrazines. Although porphyrinsand phthalocyanines have been well studied, porphyrazines have received considerably lessattention since their first synthesis almost fifty years ago. With the recent introduction ofefficient syntheses of soluble derivatives, however, porphyrazines promise to gain inprominence over their structural relatives. Porphyrins, phthalocyanines, and porphyrazinescoordinate an extensiverange of metal ions within their central cavities. In contrast toporphyrins, meso-substitution of nitrogen it tetraazaporphyrins modulates the electroniccharacter of the macrocycle. Combining the electronic character and extended π-system ofphthalocyanines and porphyrazine: with peripheral metal coordination permits the preparationof a wide variety of multimetallic complexes with novel structural, spectroscopic, magnetic,and electronic properties.In this work, our aim has been to prepare novel porphyrazines which include eight 9-anthracenecarboxylic acid groups at their periphery. Peripherally-functionalizedporphyrazines have the potential to exhibit novel optical, magnetic and electronic properties.The starting material, 1,2-bis(hydroxyethylthio)maleonitrile has been obtained from thereaction of disodium salt, 2-bromoethanole and ethanol in three days. MgPz (P4) has beensynthesized through the cyclotetramerization reaction of magnesium and n-prophanol withbis(2-hydroxyethylthio)maleonitrile. In order to convert MgPz to target macrocycle, 9-anthracenecarboxy substitued porphyrazines (P5), 9-anthracenecarboxylic acid was used inthe presence of dicyclohexyldicarbodiimide to esterifize all the eight OH groups on theporphyrazine molecule .Oktakis(9-antrhracenecarboxy) substitued porphyrazinato magnesium is suitable to prepareporphyrazines with different metal ions in the core.The usual method of treatment withtrifloro acetic acid led to metal free derivative which was further reacted with zinc (II) acetateto get metal porphyrazine ((MPz, Zn (P7)). These new compounds have been investigated andcharacterized by UV, FT-IR ve 1H NMR analysis methods. And also fluorescence emisionmeasurements of ANCOOH, MgPz and MgAntPz has been performed.Keyword : porphyrazine, tetraazaporphyrin, 9-antracenecarboxylic acid, fuorescenceJURY:1.Yrd.Doç.Dr. Naciye COSKUN (Supervisor) Date:28.09.20052.Prof.Dr.Ahmet GÜL Pages:963.Prof.Dr.Sabiha MANAV