Département de chimie moléculaire

This work describes the synthesis of a novel zinc(II) porphyrin complex, namely [Meso-4α-tetra-(1,2,3-triazolyl)phenylporphyrinato]zinc(II) symbolized by 4α-[Zn(TAzPP)] (4), using the click chem. approach in the presence of copper iodide. All of the synthetic porphyrin species reported herein were fully characterized by elemental anal., IR spectroscopy, proton NMR, UV-visible spectroscopy, and fluorescence. To synthesize the 4α-[Zn(TAzPP)] complex (4), we produced 4α-Meso-tetra-o-nitrophenylporphyrin (H2TNO2PP) and 4α-meso-tetra-o-aminophenylporphyrin (4α-H2TNH2PP) (1) using known classic literature methods. This 4α atropisomer was converted to 4α-meso-tetra-o-azidophenylporphyrin (4α-H2TN3PP) (3) by reaction with sodium nitrite and sodium azide, and then it was metalated by Zn(II), leading to [4α-meso-tetra(2-azidophenyl)porphyrinate]zinc(II) (4α-[Zn(TN3PP)]) (3). The click chem. synthetic method was finally used to prepare 4α-[Zn(TAzPP)] (4). This new tetracoordinated zinc(II) porphyrin complex was prepared and characterized in order to: (i) produce a receptor for anion recognition and sensing application for Cl- and Br-; (ii) study the catalytic decomposition of rhodamine B (RhB) and methyl orange (MO) dyes; and (iii) determine the electronic characteristics as a photovoltaic device. Complex (4) formed 1:1 complex stoichiometric species with chloride and bromide halides and the average association constants of the 1:1 addicts were ∼ 103. The photodecomposition of RhB and MO dyes in the presence of complex (4) as a catalyst and mol. oxygen showed that complex (4) presented a photodegradation yield of approx. 70% and could be reused for five successive cycles without any obvious change in its catalytic activity. The current-voltage characteristics and impedance spectroscopy measurements of complex (4) confirmed that our zinc(II) metalloporphyrin could be used as a photovoltaic device.