Département de chimie moléculaire

The synthesis of the new meso-porphyrin, tetrakis[4-(benzoyloxy)phenyl]porphyrin (H2TPBP), the meso-(tetrakis[4-(benzoyloxy)phenyl]porphyrinato)zinc(II) starting material complex [Zn(TPBP)] (1) and the 1,4-diazabicyclo[2.2.2]octane (dabco), pyrazine (pyz), 4,4'-bipyridine (4,4'-bpy), 4,4'-diaminodiphenylmethane (4,4'-mda) and the 4-cyanopyridine (4-CNpy) coordination compds. with the TPBP porphyrinate complexes (1-7, resp.) are described. The pyrazine deriv. crystallizes as bis-pyrazine six-coordinated Zn metalloporphyrin (4). Complex 5 is present in the solid state as a dimer with the 4,4'-bpy acting as a bridging ligand while in the solid state, the 4,4'-mda species (6) is a five-coordinated monomer Zn deriv. All structures of 2-6 possess cavities with different dimensions where are located the solvent mols. The soln. UV/visible spectra of 2-7 exhibit red shifted Soret bands indicating that these derivs. in soln. are five-coordinated Zn(II) porphyrin complexes. The 1H NMR of these species also confirms this deduction. The photophys. proprieties of 1-7 are similar to those of Zn(II) meso-porphyrins related species. The cyclic voltammetry of the H2TPBP free base and 1-7 present a third 1-electron reversible oxidn. wave. Single-layer diode devices of the [iridium tin oxide/zinc porphyrins (1-7)/Al] configurations show relatively low turn-on voltages. [on SciFinder(R)]