Peripherally tetra 1,2,4-triazol substituted novel phthalocyanines: Synthesis, characterization, electrochemical and spectroelectrochemical properties

Abstract

In this study, the synthesis, electrochemical and spectroelectrochemical properties of new peripherally 1,2,4-triazole substituted metal-free 4, Zn(II) 5, Ti(IV) 6, Ni(II) 7 and Co(II) 8 phthalocyanine derivatives were reported. Voltammetric and in situ spectroelectrochemical characterization of the complexes were performed in solution. Since nickel and zinc phthalocyanines gave common phthalocyanine ring based electron transfer reactions with the characteristic “energy gaps”, “peak to peak potential separations” and “half wave peak potential values”, CoII and TiIVO metal ions behaved as redox active cations in the core of the cobalt and titanium phthalocyanine complexes, respectively. While cobalt phthalocyanine gave a one-electron [CoIIPc-2]/[CoIPc-2]-1 reduction reaction, titanium phthalocyanine illustrated two metal based reduction reactions, [TiIVOPc-2]/[TiIIIOPc-2]-1 and [TiIIIOPc-2]-1/[TiIIIOPc-2]-2, in addition to the Pc ligand reduction processes. Electron transfer reactions altered the spectra of the complexes considerably, which is one of the most important expectations for the practical applications of the complexes especially in display technologies. Redox and spectral responses of cobalt and titan complexes were affected by the molecular oxygen present in the electrolyte, which indicates electrocatalytic and electrosensing activity of the complexes towards the molecular oxygen.

Keywords

• oxygen reduction reaction
• spectroelectrochemistry
• phthalocyanines
• electrosensor
• titanium

Periferal tetra 1,2,4,-triazol sübstitüe yeni ftalosiyaninler: sentez, karakterizasyon, elektrokimyasal ve spektroelektrokimyasal özellikler

Öz

Bu çalışmada, yeni peripheral 1,2,4-triazol substitue metalsiz 4, Zn(II) 5, Ti(IV) 6, Ni(II) 7 ve Co(II) 8 ftalosiyanin türevlerinin sentezi, elektrokimyasal ve spektroelektrokimyasal özellikleri rapor edilmiştir. Komplekslerin voltametrik ve in situ spektroelektrokimyasal karakterizasyonu çözelti içinde gerçekleştirildi. Nikel ve çinko ftalosiyaninler karakteristik   olarak ortak “enerji aralığı”,” pikten pike potansiyel ayrımlar” ve “yarım dalga pik potansiyel değerleri” ile ftalosiyanin halka bazlı elektron transfer reaksiyonu verirken, kobalt ve titanyum ftalosiyanin komplekslerinin kavitesinde bulunan CoII ve TiIVO metal iyonları redoks aktif katyon olarak davranmıştır. Kobalt ftalosiyanin indirgenme reaksiyonunda bir elektron [CoIIPc-2]/[CoIPc-2]-1 verirken, titanyum ftalosiyanin Pc ligand indirgenme işlemine ek olarak, iki tane metal bazlı indirgenme reaksiyonu [TiIVOPc-2]/[TiIIIOPc-2]-1 ve [TiIIIOPc-2]-1/[TiIIIOPc-2]-2 göstermiştir. Elektron transfer reaksiyonları komplekslerin spektrumlarını oldukça değiştirmiştir. Bu durum komplekslerin özellikle görüntüleme teknolojisinde pratik uygulamalarda en önemli beklentidir. Kobalt ve titanyum komplekslerinin redoks ve spektral yanıtları elektrolitte var olan moleküler oksijen tarafından etkilenmiştir. Bu da komplekslerin moleküler oksijene karşı elektrokatalitik ve elektosensör aktivitesini göstermektedir.

Anahtar Kelimeler

• Ftalosiyanin
• oksijen indirgenme reaksiyonu
• spektroelektrokimya
• elektrosensör
• titanyum

Kaynakça

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