RESUMO
Novel mononuclear Zn(ii) 4, Co(ii) 5 and Cu(ii) 6 metallophthalocyanines have been synthesized from 4,4'(ethane-1,1-p-phenol-2,2-p-phenoxy)phthalonitrile 3, which can be obtained by the reaction of 4-nitrophthalonitrile 1 with 1,1,2,2-tetrakis(p-hydroxy-phenyl)-ethane 2. The target water-soluble derivatives of 7-9 were acquired from a boiling suspension of the compounds in aqueous 20% KOH solution. The synthesized complexes have been characterized by UV-vis, IR, (1)H NMR and MALDI-TOF-mass spectroscopies. In addition, the geometric and electronic structures of 2-6 were investigated by ab initio/DFT quantum mechanical calculations using the Gaussian 03 program with HF theory at the B3LYP/3-21G level. The redox properties of the complexes 4-6 were examined by cyclic voltammetry on platinum in DMSO/TBAP. These complexes displayed one-electron metallophthalocyanine-based and multi-electron hydroxyphenyl-based redox processes. The effect of temperature on the d.c. conductivity and impedance spectra of spin coated films of compounds were investigated at the temperatures between 300-452 K and in the frequency range of 40-105 Hz. Thermally activated conductivity dependence on temperature was observed for all compounds. A.c. results indicated that conduction mechanism can be explained by classical hopping barriers mechanism for all films.
