Gemini-type 1(4),8(11)-15(18),22(25)-fluoroprobe attached as macrocyclically electrovalent mononuclear and bunk-type dinuclear phthalocyanines

Abstract

The new gemini designed 1(4),8(11)-15(18),22(25)-fluoroprobe attached macrocyclically electrovalent mononuclear [(Co(II) (2a), Mn(III) (3a)] and bunk-type (dimer) electrovalent dinuclear [(Co(II) (2b), Mn(III) (36)] phthalocyanines have been synthesized as a mixture from the corresponding 3,3'-(1,1'-((4-methoxy phenyl)methylene)bis(naphthalene-2,1-diyl))bis(oxy)-diphthalonitrile (1), an adjacent bis dinitrile, which is obtained from the reaction of 3-nitrophthalonitrile and 1,1'-((4-methoxyphenyl)methylene)dinaphthalen-2-ol. The extraordinary mono and dinuclear types of phthalocyanines have been separated from each other by tedious purification using their different dissolution capabilities. FTIR, H-1 NMR, C-13 NMR, UV-Vis, MALDI-TOF/MS spectral, magnetic susceptibility and elemental analysis data have been used to characterize the novel compounds. The magnetic susceptibility studies revealed that all of the mono and dinuclear complexes are paramagnetic and high-spin complexes. The spectroscopic properties of the complexes, which are organo-soluble, are affected strongly by the fluorescent units on the periphery of the phthalocyanines. The fluorescence quantum yield was affected by the molecular structures of the mono and dinuclear manganese phthalocyanines (3a and 3b), and this is discussed. It was found that the cage effect diminished the fluorescence quantum yield of the phthalocyanine structure. The redox behavior of the complexes was examined by voltammetry on Pt in DMSO/TBAP. The electrochemical measurements showed the formation of pronounced-valence oxidation and reduction species with potential shifts. (C) 2013 Elsevier Ltd. All rights reserved.