Synthesis,Characterization and Investigation of Electrochemical and Spectroelectrochemical Properties of Peripherally Tetra Diethoxypropan Substituted Phthalocyanines

In this study novel peripherally tetra 1,3-diethoxy-2-propanol substituted Co(II), Cu(II), Mg(II), Ni(II) Zn(II) phthalocyanine derivatives were prepared. The characterization of the novel compounds was made by FT-IR, ¹H-NMR, UV-vis and MALDI-TOF mass. Electrochemical, in-situ spectroelectrochemical and electrocolorimetric measurements have been carried out with the aim to determine the redox properties, to illuminate reaction mechanism and the effect of substituent and metal center. Moreover, the color properties and aggregation tendency of compounds were also investigated.     

Synthesis, in situ spectroelectrochemical, in situ electrocolorimetric and electrocatalytic investigation of brown-manganese phthalocyanines

α- and β-substituted tetrakis(6-hydroxyhexylthiol) phthalocyaninato manganese (III) chloride complexes have been prepared via cyclotetramerization. Both complexes have been characterized by elemental analysis, FTIR, MS and UV–Vis spectral data. The voltammetric and in situ spectroelectrochemical studies reveal that both complexes exhibit an oxidation and three reduction processes having reversible, one-electron, and diffusion controlled mass transfer characteristics, which are assigned to Mn^IIIPc²⁻/Mn^IVPc²⁻, Mn^IIIPc²⁻/Mn^IIPc²⁻, Mn^IIPc²⁻/Mn^IPc²⁻, and Mn^IPc²⁻/Mn^IPc³⁻ couples respectively. The existence of oxygen in solution significantly affects the in situ spectroelectrochemical behavior of the complexes due to the formation of μ-oxo MnPc species. An in situ electrocolorimetric method has been applied to investigate the colors of the electro-generated anionic and cationic forms of the complexes for the first time in this study. The complexes, coated on a glassy carbon electrode potentiostatically, show considerable high electrocatalytic activity to hydrogen evolution reactions in aqueous solution.     

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 = Zn^II, Co^II, Mn^IIICl, Fe^IIIAc, Cu^II) 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 Ag^I and Pd^II, 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 Ag^I and Pd^II 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.