Spectroscopy and electronic structure of electron deficient zinc phthalocyanines

Steven P. Keizer, John Mack, Barbara A. Bench, Sergiu M. Gorun, Martin J. Stillman

研究成果: Article査読

73 被引用数 (Scopus)

抄録

The effect of introduction of perfluoro alkyl groups into phthalocyanines, as evidenced by the spectroscopic properties of 1,4,8,11,15,18,22,25-octa-fluoro-2,3,9,10,16,17,23,24-octa-perfluoro isopropyl zinc phthalocyanine, ZnF64Pc(-2) and its ring-reduced radical anion species, [ZnF64Pc(-3)]-, are reported. A combination of UV-visible absorption and magnetic circular dichroism (MCD) spectroscopy, ESI and MALDI-TOF mass spectrometry, cyclic and differential pulse voltammetry, and complete theoretical calculations using INDO/S and DFT techniques reveals that the substitution of all sixteen hydrogen atoms in protio ZnPc(-2) by eight F and eight i-C3F7 groups red shifts the Q and π → π* transitions and narrows the HOMO-LUMO gap while simultaneously preventing ring photooxidation and stabilizing the radical anion. The [ZnF64Pc(-3)]- species, which is in equilibrium in solution with the neutral complex when a reducing agent is present, is unusually stable. The above effects are attributed to the strong electron withdrawing properties of the peripheral substituents, which render ZnF64Pc extremely electron deficient.

本文言語English
ページ(範囲)7067-7085
ページ数19
ジャーナルJournal of the American Chemical Society
125
23
DOI
出版ステータスPublished - 2003 6月 11

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

フィンガープリント

「Spectroscopy and electronic structure of electron deficient zinc phthalocyanines」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル