Preparation of phthalocyanines fused with four tetrathiafulvalene units via the functional group transformation of tetrakis(o-xylylenedithio)phthalocyanines with toluene/aluminum chloride

Abstract

Tetrakis(o-xylylenedithio)phthalocyanine 5 and its nickel complex 5-Ni were treated with aluminum chloride in toluene to eliminate the peripheral o-xylylene groups. The thiolate anions generated from 5 and 5-Ni were reacted with carbonyldiimidazole to produce phthalocyanines 6 and 6-Ni with four 1,3-dithiole-2-one rings, respectively. Phthalocyanine 7a having four ethylenedithiotetrathiafulvalene units was prepared via the condensation of 6-Ni with ethylenedithio-1,3-dithiole-2-thiones. The reaction of 6-Ni with bis(methylthio)-1,3-dithiole-2-thiones gave phthalocyanine 7b with the corresponding TTF units. The structures of the products were determined by 1 H NMR and MALDI-TOF-MS. Their electrochemical and optical properties were examined by cyclic voltammetry and UV-vis spectroscopy.