Synthesis and characterization of metallo and metal-free octaalkylphthalocyanines and uranyl decaalkylsuperphthalocyanines

A straightforward, efficient, and generalizable 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 n-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.