Syntheses and nonlinear optical properties of nonaggregated metallophthalocyanines

Hexadecakis(2,2,2-trifluoroethoxy)-substituted vanadyl and zinc phthalocyanines, and hexadecakis(ethoxy)vanadylphthalocyanine, were synthesized and characterized. Their aggregation properties were studied by evaluation of the concentration dependence of absorption spectra. Hexadecakis(2,2,2-trifluoroethoxy)-substituted metallophthalocyanines were found to be nonaggregated phthalocyanines even in the condensed state. However, nonfluorinated hexadecakis(ethoxy)vanadylphthalocyanine showed a redshift of the Q band in the solid state. The third-order nonlinear optical properties of these phthalocyanine films were studied by electroabsorption measurement in terms of molecular structure and aggregation. The aggregation effect enhances the macroscopic third-order nonlinearity of metallophthalocyanine. Among nonaggregated hexadecakis(2,2,2-trifluoroethoxy)-substituted metallophthalocyanines, zinc phthalocyanine was found to have a larger macroscopic third-order nonlinearity than the vanadyl compound.