Amino Group Position Dependent Orientation of Self-Assembled Monomolecular Films of Tetraaminophthalocyanatocobalt(II) on Au Surfaces

Abstract

Self-assembled monomolecular films of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4alpha-CoIITAPc) and 2,9,16,23-tetraaminophthalocyanatocobalt(II) (4beta-CoIITAPc) on Au surfaces were prepared by spontaneous adsorption from solution. These films were characterized by cyclic voltammetry and Raman spectroscopy. Both the surface coverage (Gamma) and intensity of the in-plane stretching bands obtained from Raman studies vary for these monomolecular films, indicating different orientations adopted by them on Au surfaces. The 4alpha-CoIITAPc-modified electrode exhibits an E1/2 of 0.35 V, while the 4beta-CoIITAPc-modified electrode exhibits an E1/2 of 0.19 V, corresponding to the CoII/CoIII redox couple in 0.1 M H2SO4. The Gamma estimated from the charge associated with the oxidation of Co(II) gives (2.62 +/- 0.10) x 10-11 mol cm-2 for 4alpha-CoIITAPc and (3.43 +/- 0.14) x 10-10 mol cm-2 for 4beta-CoIITAPc. In Raman spectral studies, the intensity ratio between in-plane phthalocyanine (Pc) stretching and the Au-N stretching was found to be 6.6 for 4beta-CoIITAPc, while it was 1.6 for 4alpha-CoIITAPc. The obtained lower Gamma and intensity ratio values suggest that 4alpha-CoIITAPc adopts nearly a parallel orientation on the Au surface, while the higher Gamma and intensity ratio values suggest that 4beta-CoIITAPc adopts a perpendicular orientation. The electrochemical reduction of dioxygen was carried out using these differently oriented Pc's in phosphate buffer solution (pH 7.2). Both the Pc's catalyze the reduction of dioxygen; however, the 4alpha-CoIITAPc-modified electrode greatly reduces the dioxygen reduction overpotential compared to 4beta-CoIITAPc-modified and bare Au electrodes.