Spectroscopy and electronic structure of electron deficient zinc phthalocyanines

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

Research output: Contribution to journalArticlepeer-review

70 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)7067-7085
Number of pages19
JournalJournal of the American Chemical Society
Volume125
Issue number23
DOIs
Publication statusPublished - 2003 Jun 11

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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