title: Spectroscopy and electronic structure of electron deficient zinc phthalocyanines.
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, ZnF(64)Pc(-2) and its ring-reduced radical anion species, [ZnF(64)Pc(-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-C(3)F(7) groups red shifts the Q and pi --> pi transitions and narrows the HOMO-LUMO gap while simultaneously preventing ring photooxidation and stabilizing the radical anion. The [ZnF(64)Pc(-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 ZnF(64)Pc extremely electron deficient.
authors.affiliation: Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7 Canada.
authors.forename: Steven P
authors.initials: SP
authors.lastname: Keizer
authors.forename: John
authors.initials: J
authors.lastname: Mack
authors.forename: Barbara A
authors.initials: BA
authors.lastname: Bench
authors.forename: Sergiu M
authors.initials: SM
authors.lastname: Gorun
authors.forename: Martin J
authors.initials: MJ
authors.lastname: Stillman