Peripheral and non-peripheral-designed multifunctional phthalocyanines; synthesis, electrochemistry, spectroelectrochemistry and metal ion binding studies

A novel type of ionophore ligands, 3′-(2,3-dihydroxypropylthio)-phthalonitrile and 4′(2,3-dihydroxypropylthio)-phthalonitrile, and their α- and β-tetrasubstituted metallo phthalocyanines, (MPc), (M = ZnII, CoII, MnIIICl, FeIIIAc, CuII) have been prepared and fully characterized by elemental analysis, FT-IR, 1H and 13C NMR, and MS (ESI and Maldi-TOF). The complexes are soluble in both polar and non-polar solvents, such as MeOH and EtOH, THF, CHCl3 and CH2Cl2. The spectroscopic properties of the complexes are affected strongly by the electron-donating sulfanyl units on the periphery of the phthalocyanines. The cation binding properties of the complexes, for example using AgI and PdII, were evaluated by UV–Vis spectroscopy and the results show the formation of polynuclear phthalocyanine complexes. Functional donors on the periphery of the zinc and copper complexes coordinate to AgI and PdII to give ca. a 2:1 metal–phthalocyanine complex binding ratio for the concentration of 2.5 × 10−5 M (Pc) and 1.0 × 10−3 M (Metal ions). Voltammetric and in-situ spectroelectrochemical studies were performed to characterize the redox behavior of the complexes. An in-situ electrocolorimetric method was applied to investigate the colors of the electro-generated anionic and cationic forms of the complexes.

A novel type of ionophore ligands, 3′-(2,3-dihydroxypropylthio)-phthalonitrile and 4′(2,3-dihydroxypropylthio)-phthalonitrile, and their α- and β-tetrasubstituted metallo phthalocyanines, (MPc), (M = ZnII, CoII, MnIIICl, FeIIIAc, CuII) have been prepared and fully characterized by elemental analysis, FT-IR, 1H and 13C NMR, and MS (ESI and Maldi-TOF). The cation binding abilities of the complexes with AgI, and PdII were evaluated by UV–Vis spectroscopy and the results show the formation of polynuclear phthalocyanine complexes. Voltammetric and in-situ spectroelectrochemical studies were performed to characterize the redox behavior of the complexes. An in-situ electrocolorimetric method was applied to investigate the colors of electro-generated anionic and cationic forms of the complexes.Figure optionsDownload as PowerPoint slideResearch highlights
► 3’- and 4’-(2,3-dihydroxypropylthio)-phthalonitrile, and their sensor MPcs were prepared.
► Characterized by EA, UV–Vis, FT-IR, 1H and 13C-NMR, MS (ESI and Maldi-TOF).
► Their cation binding properties such as, AgI and PdII resulted in a dimeric assembly.
► The mole binding ratio were found to be ca. 2:1 for [AgI]/[M(Pc)(M = Zn, Cu)].
► The voltammetric and in-situ spectroelectrochemical studies were performed.