Synthesis and Characterization of Metallo and Metal-Free Octaalkylphthalocyanines and Uranyl Decaalkylsuperphthalocyanines

A straightforward, efficient, and generalizadle synthesis of symmetrically substituted 2, 3, 9, 10, 16, 17, 23, 24-octaalkylphthalocyanines and uranyl 2, 3, 9, 10, 16, 17, 23, 24, 30, 31 -decaalkylsuperphthalocyaninates from o-dialkylbenzenes is described. For phthalocyanines, the approach is illustrated for methyl and zi-butyl substituents, and both metal-free and nickel complexes are reported. Uranyl superphthalocyanines have been prepared with methyl and n-butyl substituents. The new complexes have been characterized by a variety of chemical and physicochemical methods. Quantitative determination of the solubilities of substituted and unsubstituted phthalocyanine and superphthalocyanine complexes in both 1, 2, 4-trichlorobenzene and toluene demonstrates decreasing solubility in the order (4, 5-Bu₂)₅SPcUO₂ > (4-Me)₅SPcUO₂ > (4, 5-Me₂)₅SPcUO₂ > SPcUO₂ > (4-Me)₄PcH₂ > Ni(4, 5-Bu₂)Pc > Ni(4, 5-Me₂)₄Pc > NiPc. Attempts to displace the uranyl ion from (4, 5-R₂)₅SPcUO₂ with acids or Cu(OAc)₂ lead to the formation of (4, 5-R₂)₄PcH₂ or Cu(4, 5-R₂)₄Pc, respectively.