Diskotik makromoleküllerin sentezi ve metal komplekslerinin incelenmesi
The synthesis of discotic macromoleculers and investigation of their metal complexes
Yazar: ÖZCAN KOÇYİĞİT
Danışman: YRD. DOÇ. DR. ERSİN GÜLER
Selçuk Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Doktora, 2009
Konu: Kimya = Chemistry
Dizin: Schiff bazları = Schiff bases ; Sıvı kristaller = Liquid crystals

Özet:
Bu çalışmanın birinci bölümümde çıkış maddesi olarak, 1,2-dimetoksibenzen (veratrol) kullanıldı. Veratrol, susuz demir(III)klorür ve diklormetanlı ortamda literatürde verilen metoda göre trimerizasyon reaksiyonuna tabi tutuldu ve 2,3,6,7,10,11- hekzametoksitrifenilen sentezlendi. Bu bileşiğe daha sonra BBr3 ile muamele edilerek 2,3,6,7,10,11-hekzahidroksitrifenilen sentezlendi. Sentezlenen trifenilen çekirdek ile; etilbromoasetat, metil(4-bromometil)benzoat, metil 5-bromovalereat ve metil 6-bromovalereat sıvı kristal özellik gösterebilen liganları elde edildi.Sentezlenen bu ligandlar HCl ile etkileştirilip, daha sonra etanollü ortamda [{Fe(Salen)}2O], [{Cr(Salen)}2O], [{Fe(Saloph)}2O], [{Cr(Saloph)}2O] köprü kompleksleri ile reaksiyona tabi tutularak yeni Fe(III) ve Cr(III) kompleksleri elde edildi. Ayrıca bu trifenilen çekirdeğe 2-[(2-Kloroetilimino)metil]fenol Schiff bazı bağlanarak sentezlenen liganda, etanollü ortamda Co(II), Cu(II), Ni(II), Zn(II), Pd(II) ve Cd(II) asetat tuzları ilave edilerek bu ligandların renkli kompleksleri elde edildi.Bu çalışmanın ikinci bölümümde çıkış maddesi olarak 1,3,5-tris(bromometil)benzen kullanıldı. 1,3,5-Tris(bromometil)benzen K2CO3 ve asetonitrilli ortamda 4-hidroksibenzaldehit ile reaksiyona girerek, 1,3,5-tris(formilfenoksimetil)benzen (TRIPOD) elde edildi. Bu bileşiğin benzer literatürlerden faydalanarak çeşitli aminler ile kenetlenme reaksiyonu verdirilmesi sonucu Tripodal Schiff bazları sentezlendi. Tripodal Schiff bazlarının sentezi için 5-aminoisoftalikasit, 4-aminobenzoikasit ve 4-nitroanilin molekülleri kullanıldı. Daha sonra etanollü ortamda [{Fe(Salen)}2O], [{Cr(Salen)}2O], [{Fe(Saloph)}2 O], [{Cr(Saloph)}2 O] köprü kompleksleri ile reaksiyona tabi tutularak yeni Fe(III) ve Cr(III) kompleksleri elde edildi.Sonuç olarak trifenilen çekirdekli beş, tripod çekirdekli üç toplam sekiz farklı ligand ve kompleksleri izole edilerek, elementel analizleri, FT-IR, 1H-NMR, manyetik süsseptibilite ve TGA/DTG spektrumları alınarak yapıları aydınlatıldı.

Abstract:
In the first part of this study, 1,2-dimethoxybenzene (veratrole) was used as an initial reagent. According to the literature, 2,3,6,7,10,11- hexamethoxytriphenylene was synthesized by the trimerisation reaction of veratrol and nonaqueous iron(III)chloride in dichloromethane medium. This compound was then treated with BBr3 and the resulting 2,3,6,7,10,11-hexahydroxytriphenylene compound was obtained. That triphenylene compound was reacted with each of the ethylbromoacetate, methyl(4-bromomethyl)benzoate, methly 5-bromovalerate and methyl 6-bromovalerate reactants ligands which show liquid crystal property were synthesized.After the esteric ends of these ligands were acidified, in ethanol medium, new complexes of Fe(III) and Cr(III) were obtained by the reaction of ligands and these following bridged complexes; [{Fe(Salen)}2O], [{Cr(Salen)}2O], [{Fe(Saloph)}2 O], [{Cr(Saloph)}2 O]. Additionally, 2-[(2-chloroethylimino)methyl]phenol Schiff base was bonded to that triphenylene compound and in ethanol medium, acetate salts of Co(II), Cu(II), Ni(II), Zn(II), Pd(II) and Cd(II) were added seperately to that ligand solution to make colorful complexes.In the second part of this study, 1,3,5-tris(bromomethyl)benzene was used as an initial reagent. 1,3,5-tris(bromomethyl)benzene was reacted with 4-hydroxybenzaldehyde in K2CO3 and acetonitrile medium to obtain 1,3,5-tris(formylphenoxymethyl)benzene (TRIPOD). According to the literature, as a result of the coupling reactions of that ligands and different amine compounds Tripodal schiff bases were synthesized. 5-Aminoisophtalicacid, 4-aminobenzoicacid and 4-nitroaniline molecules were used for these synthesis. Then, in ethanol medium new complexes of Fe(III) and Cr(III) were obtained by the reaction of that Schiff bases and these following bridged complexes; [{Fe(Salen)}2O], [{Cr(Salen)}2O], [{Fe(Saloph)}2 O], [{Cr(Saloph)}2 O].As a result, five triphenylene compounds, three TRIPOD compounds, as a total eight different ligands and their complexes were isolated and by using FT-IR, 1H-NMR, magnetic susceptibility and TGA/DTG their elemental analysis were performed.