TY - JOUR
T1 - Spectroscopy and electronic structure of electron deficient zinc phthalocyanines
AU - Keizer, Steven P.
AU - Mack, John
AU - Bench, Barbara A.
AU - Gorun, Sergiu M.
AU - Stillman, Martin J.
PY - 2003/6/11
Y1 - 2003/6/11
N2 - 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.
AB - 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.
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U2 - 10.1021/ja0299710
DO - 10.1021/ja0299710
M3 - Article
C2 - 12783561
AN - SCOPUS:0038517992
VL - 125
SP - 7067
EP - 7085
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 23
ER -