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

Abstract

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