Synthesis and characterization of novel phthalocyanines with four tridentate NNS substituents and four chloro groups

Two new 4,5-disubstituted phthalonitrile derivatives have been prepared fro m tridentate amine thiol reactants obtained by reducing directly two differ ent benzothiazolines. Novel metal free phthalocyanines and divalent metal p hthalocyanines carrying four tridentate NNS substituents in addition to fou r chloro groups on peripheral positions have been synthesized from the corr esponding phthalonitrile derivatives in the presence of a suitable anhydrou s metal salt [Zn(CH3CO2)(2) or NiCl2] or 2-(dimethylamino)ethanol. A luteti um(III) bis(phthalocyaninate) complex that is highly soluble in most organi c solvents has been synthesized from reaction of one of the phthalonitrile derivatives with anhydrous lutetium(III) acetate in the presence of 1,8-dia zabicyclo[5.4.0]undec-7-ene (dbu) in 1-hexanol. The newly synthesized compo unds have been characterized by elemental analyses, IR, H-1, C-13 NMR, MS, UV/VIS, ESR, and atomic absorption spectroscopy. Cyclic voltammetric measur ements of the novel compounds have been made.