title: 2,3,9,10,16,17,24,25-Octakis(octyloxycarbonyl)phthalocyanines. Synthesis, spectroscopic, and electrochemical characteristics.
abstract: A series of three novel 2,3,9,10,16,17,24,25-octakis(octyloxycarbonyl)phthalocyanine compounds M[Pc(COOC8H17)8] (M = 2H, Cu, Zn) (1-3) have been synthesized via the cyclic tetramerization of 4,5-di(octyloxycarbonyl)phthalonitrile, which was obtained by a newly developed procedure with o-xylene as starting material, promoted with organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the absence and presence of metal salt like M(acac)2.H2O (M = Cu, Zn) in n-octanol at 120 degrees C. In addition to elemental analysis, these novel octakis(octyloxycarbonyl)-substituted phthalocyanine compounds have been characterized by a series of spectroscopic methods. The electrochemistry of these compounds was also studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. A significant shift to the positive direction for both the first oxidation and the first reduction of compound 1, relative to H2Pc, reveals the electron-withdrawing nature of octyloxycarbonyl groups attached to the peripheral positions of phthalocyanine. The effect of peripheral octyloxycarbonyl substitution on the electrochemistry of the series of phthalocyanines 1-3 has been reasonably explained by theoretical calculation results using the density functional theory (DFT) method.
authors.affiliation: Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan 250100.
authors.forename: Xueying
authors.initials: X
authors.lastname: Wang
authors.forename: Yuexing
authors.initials: Y
authors.lastname: Zhang
authors.forename: Xuan
authors.initials: X
authors.lastname: Sun
authors.forename: Yongzhong
authors.initials: Y
authors.lastname: Bian
authors.forename: Changqin
authors.initials: C
authors.lastname: Ma
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang