Yeni Esnek Ditiya-alkil Köprülü Homo-dimerik Metalsiz ve Metalli ftalosyaninler

Öz

Bu çalışmada,  homo dimerik metal içermeyen ve metaloftalosiyaninlerin organik çözücülerde spektroskopik özelliklerinin sentezi, karakterizasyonu ve araştırılması gerçekleştirilmiştir. Ftalosiyaninlerin sentezi için başlangıç ​​bileşiği olarak seçilmiş diftalonitril türevi, 4-nitroftalonitril ve bileşik l'in kuru dimetilformamid / potasyum karbonat içinde reaksiyonu ile hazırlandı. 1:6.15 oranında ftalonitril ile substitue diftalonitrilin siklotetramerasizasyonu, beklenen homo-dimerik metal içermeyen ftalosiyanini ve Zn(II), Ni(II), Co(II) ve Cu(II) metal tuzları ile tetramerizasyonu da, binükleer Zn-, Ni-, Co- and Cu- ftalosyaninleri oluşturdu. Tüm bu reaksiyonlar, DMAE/1,8-diazabicyclo [5.4.0] undec-7-ene sisteminde gerçekleştirildi. Ürünler, kristallendirme ve silika jel kolon kromatografisi ile saflaştırıldı. Yeni hazırlanan bileşikler,  IR, 1H / 13C-NMR, MS ve UV-Vis spektroskopisinin kombinasyonu ile karakterize edildi. Ayrıca, tüm yeni ftalosiyaninlerin agregasyon davranışları da araştırılmıştır. Metal içermeyen metalli-ftalosiyaninlerin agregasyon özellikleri kloroformda araştırılmıştır. Dimerik metal içermeyen metalli-ftalosiyaninler kloroformda 4x10-6-16x10-6 mol/L konsantrasyon aralığında agregasyon göstermemiştir. Ayrıca kloroform, N,N-dimetil formamid, dimetilsülfoksit, piridin ve tetrahidrofuranda Co-ftalosiyanin molekülünün agregasyon özellikleri araştırılmıştır. Co-ftalosiyanin molekülü, 1x10-5 mol/L konsantrasyonda belirtilen çözücülerde monomerik davranış göstermiştir.

Anahtar Kelimeler

• agregasyon
• dimerik ftalosiyanin
• ftalosiyanin
• sentez
• spektroskopi

Novel Flexible Dithia-alkyl Bridged Homo-dimeric Metal-free and Metallophthalocyanines

Abstract

In this study, synthesis, characterization and investigation of spectroscopic properties in organic solvents of homo dimeric metal free and metallophthalocyanines have been carried out. The substituted di-phthalonitrile derivative as a starting material for the synthesis of phthalocyanines was prepared by the reaction of 4-nitrophthalonitrile and compound 1 in dry dimethylformamide/potassium carbonate. The cyclotetramerization of substituted diphthalonitrile derivative with phthalonitrile in 1:6.15 ratio gave the expected homo-dimeric metal-free phthalocyanine and with metal salts of Zn(II), Ni(II), Co(II) and Cu(II) gave binuclear Zn-, Ni-, Co- and Cu-phthalocyanines, respectively, in dimethyl aminoethanol/1,8-diazabicyclo [5.4.0] undec-7-ene system. The products were purified by crystallization and silica gel column chromatography. The newly prepared compounds were characterized by a combination of IR, 1H / 13C-NMR, MS and UV-Vis spectroscopy. In addition, aggregation behaviors of all novel phthalocyanines were investigated. Aggregation properties of the metal free and metallophthalocyanines have been investigated in chloroform. Dimeric metal free and metallophthalocyanines did not show aggregation in chloroform at 4x10-6–16x10-6 mol/L concentration range. Furthermore, aggregation properties of Co- phthalocyanine have been investigated in chloroform, N,N–dimethyl formamide, dimethylsulfoxide, pyridine and tetrahydrofurane. Co-phthalocyanine complex showed monomeric behavior in mentioned solvents at 1x10-5 mol/L concentration.

Keywords

• Aggregation
• dimeric phthalocyanine
• phthalocyanine
• synthesis
• spectroscopy

References

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