Synthesis, characterization, aggregation, fluorescence, electrical and thermal properties of novel octasubstituted metal-free and metallophthalocyanines

Abstract A dinitrile precursor, 1,2-bis(3-hydroxypropylmercapto)-4,5-dicyanobenzene ( 3 ), was synthesized via base-catalyzed nucleophilic aromatic chlorine displacement of 4,5-dichlorophthalonitrile with 3-mercapto-1-propanol. A novel metal-free phthalocyanine ( 4 ) (M = 2H) and its metal complexes ( 5 )–( 8 ) (M = Zn, Ni, Cu and Co) were prepared by the cyclotetramerization reaction of ( 3 ) with the appropriate materials. The aggregation property of the zinc(II) phthalocyanine ( 5 ) was investigated in terms of concentration, Ag + , Hg 2+ , Pb 2+ and Cd 2+ cations and also different solvents, such as dimethylformamide and pyridine. Complexation of the peripheral dithia groups of ( 5 ) with Ag + or Pd 2+ yields the pentanuclear complex ( 9 ) or ( 10 ), respectively. The fluorescence spectrum of compound ( 5 ) was also studied. The electrical conductivities of ( 5 )–( 10 ) in air and under vacuum were found to be ∼10 −9 –10 −5  S m −1 . All the novel compounds were characterized by elemental analysis, UV–Vis, FT-IR, NMR and MS spectral data and DSC techniques.