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

A straightforward, efficient, and generalizable synthesis of symmetrically substituted 2,3,9,10,16,17,23,24-octaalkyl-phthalocyanines 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-Bu/sub 2/)/sub 5/SPcUO/sub 2/ > (4-Me)/sub 5/SPcUO/sub 2/ > (4,5-Me/sub 2/)/sub 5/SPcUO/sub 2/ > SPcUO/sub 2/ > (4-Me)/sub 4/PcH/sub 2/ > Ni(4,5-Bu/sub 2/)Pc > Ni(4,5-Me/sub 2/)/sub 4/Pc > NiPc. Attempts to displace the uranyl ion from (4,5-R/sub 2/)/sub 5/SPcUO/sub 2/ with acids or Cu(OAc)/sub 2/ lead to the formation of (4,5-R/sub 2/)/sub 4/PcH/sub 2/ or Cu(4,5-R/sub 2/)/sub 4/Pc, respectively.