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

Yıl 2017, Sayı: 1, 22 - 30, 31.12.2017

Ayşe Aktaş Kamiloğlu , Mehmet Aydemir İrfan Acar Gülbınar Sarkı Atıf Koca , Nurhan Gümrükçüoğlu , Ümmühan Ocak Halit Kantekin

Öz

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.

Anahtar Kelimeler

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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