SYNTHESIS AND PROPERTIES OF AROMATIC AMINE-BRIDGED PCRU(II) COORDINATION-COMPOUNDS

Three aromatic amine-bridged coordination compounds [PcRuL]n {L = p-phenylenediamine (ppd) (1a), 2,7-diaminofluorene (daf) (2a), 4-aminopyridine (apy) (3a)} were prepared by the reaction of PcRu(II) with the corresponding ligands, ppd, daf and apy, in order to study their properties as axial ligands in oxidation reactions. The compounds la, 2a and 3a were characterized by elemental analyses, C-13 CPMAS (1a, 3a), IR and UV-Vis spectroscopy and TG/DTA analyses. Oxidation (doping) of la, 2a and 3a with iodine in toluene gave the corresponding axial ligand-centred oxidation products as quinoid forms lb and 2b. In contrast, compound 3a led to the Pc-macrocycle oxidation form 3b with I5- polyiodide chain, as confirmed by Raman spectroscopy. Oxidation of 1a with H2O2/HCl and (NH4)2S2O8/HCl in aqueous solution also showed the axial ligand oxidation products 1c, 1d. The oxidized products 1b, 1c, 1d and 2b show increased conductivity between 2.1 x 10(-3) and 4.0 x 10(-6) S/cm in comparison to the precursor systems.