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Journal of Coordination Chemistry
Year: 2008  |  Volume: 61  |  Issue: 19  |  Page No.: 3147 - 3157

Synthesis and pH-sensitive redox properties of 1,10-phenanthroline-5,6-dione complexes

Ying-Ying Kou, Guang-Jun Xu, Wen Gu, Jin-Lei Tian and Shi-Ping Yan    

Abstract: Synthesis and pH-sensitive electrochemical properties of three complexes, [Cu(PD)3] · (ClO4)2 · 2.25CH3CN · 6H2O (1), [Cu(PD)(DMSO)Cl2] · DMSO · H2O (2) and [Co(PD)3] · (ClO4)2 · CH3CN · 2H2O (3) (PD=1,10-phenanthroline-5,6-dione), are reported. Single-crystal X-ray diffraction of the complexes suggest that the structure of 1 is orthorhombic, 2 triclinic and 3 orthorhombic. The electrochemical properties of free PD and the three complexes in phosphate buffer solutions in a pH range between 2 and 9 have been investigated using cyclic voltammetry. The redox potentials of these compounds are strongly dependent on the proton concentration in the range -0.3 V ∼ 0.4 V versus SCE (saturated calomel reference electrode). The reduction behavior of PD can be described from quinone species to semiquinone anion then to the fully reduced dianion. At pH < 4, the reduction of PD proceeds via 2e-/3H+ processes, while at pH > 4, the reduction of PD proceeds via 2e-/2H+. For all complexes, the N-N chelate PD ligand is electrochemically active and underwent step reduction via 2e-/2H+.

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