Synthesis, electrochemical, and spectroelectrochemical properties of tetrakis(13,17-dioxa nonacosane-15-sulphanyl) phthalocyaninato zinc(II)


Yılmaz İ., Gurek A., Ahsen V.

POLYHEDRON, cilt.24, sa.7, ss.791-798, 2005 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 24 Sayı: 7
  • Basım Tarihi: 2005
  • Doi Numarası: 10.1016/j.poly.2005.02.018
  • Dergi Adı: POLYHEDRON
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.791-798
  • Anahtar Kelimeler: phthalocyanines, electrochemistry, spectroelectrochemistry, zinc, DECKER LUTETIUM(III) PHTHALOCYANINES, TRINUCLEAR COMPLEXES BEARING, NONLINEAR-OPTICAL PROPERTIES, THIN-FILMS, SUBSTITUTED PHTHALOCYANINES, PHOTOCHEMICAL FORMATION, CATION RADICALS, METALLOPHTHALOCYANINES, ELECTROCHROMISM, REDUCTION
  • İstanbul Teknik Üniversitesi Adresli: Evet

Özet

Tetrakis(13,17-dioxa nonacosane-15-sulphanyl) phthalocyaninato zinc(II), ZnPc(SCH(CH2OR)(2))(4), where R = C12H25, was synthesised and its electrochemical and spectroelectrochemical properties were investigated in dichloromethane. The neutral complex undergoes two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in CH2CI2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The half-wave potentials for oxidation of the complex are located at E-1/2 = 0.61 and 1.38 V, while the two reductions are located at E-1/2 = -0.87 and -1.11 V versus SCE. These potentials show little or no difference compared to those of unsubstituted ZnPc and other SR substituted phthalocyanines under the same experimental conditions, thus suggesting weak electron-donating effects of the peripheral alkylthio substituents on the phthalocyanine rings. The well-defined UV-Vis spectra of electro-reduced and electro-oxidised species, [ZnPPC(-3)(SCH(CH2OR)(2))(4)](-), [ZnPc-(-4)(SCH(CH2OR)(2))(4)](2-) and [ZnPe(-1)(SCH(CH2OR)(2))(4)](+), were obtained by applied potentials (E-app = -1.04 V, E-app = -1.62 V, and E-app = 1.20 V, respectively) in a thin-layer cell. The first and second reduction products showed characteristic spectral changes corresponding to mono- and di-anionic species of zinc phthalocyanines, and the first oxidation showed spectral changes corresponding to the formation of a mono-cationic dimer. © 2005 Elsevier Ltd. All rights reserved.