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

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+, Hg2+, Pb2+ and Cd2+ cations and also different solvents, such as dimethylformamide and pyridine. Complexation of the peripheral dithia groups of (5) with Ag+ or Pd2+ 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.

Graphical abstractThe novel metal-free phthalocyanine (4) and its metal complexes (5)–(8), bearing octakis(3-hydroxypropylmercapto) substituents, have been prepared and characterized. Complexation of compound (5) with Ag+ or Pd2+ also was investigated. The electrical conductivities, thermal, aggregation and fluorescence properties of the phthalocyanines were also examined.Figure optionsDownload full-size imageDownload as PowerPoint slide