Ferrocenyl Complexes Of Unsaturated Carboxylic Acids, Structure And Performance

Currently, the rational design and synthesis of novel ferrocenyl-containing coordination polymers have received much attention due to the special chemical, stereochemical, and electrochemical properties of ferrocene. A variety of ferrocenyl complexes have been obtained which can be used as good candidates for new functional materials such as molecular sensor, and molecular magnetic and non-linear optical materials. On these bases, introducing bulky ferrocenyl carboxylate groups into the complex molecular systems and further exploiting the relationship between their structures and properties have become one of the most attractive research fields in modern material chemistry.In this paper, several ferrocenyl saturated carboxylate-containing complexes were obtained by treating ferrocenylacetate (FcCH₂COONa) or 3-ferrocenylpropionate (FcCH₂CH₂COONa) with some metal ions under the help of some bridging ligands. Additional, their syntheses, structural analyses, electrochemical properties, fluorescent properties and third-order nonlinear optical (NLO) properties were also investigated.Treatment of FcCH₂COONa with Cd(Ac)₂·2H₂O or Pb(NO₃)₂ in presence of 4,4'-bpy afforded two similar polymers 1 and 2. In the structures of them, the 4,4'-bpy ligand connects metal ions leading to a one-dimensional chain with FcCH₂COO^- units acting as chelate ligands in the side chain. However, the reaction of FcCH₂COONa with CdCl₂·2.5H₂O afforded a binuclear complex 3 when the bridging ligand 4,4'-bpy was replaced by bulkier btx. The electrochemical properties of complexes 1³ and the free ferrocene acetic acid have been investigated in the solution state. The results shown that the half-wave redox potentials of three complexes were all slightly higher than that of ferrocene acetic acid. Further investigation of the electrochemical data revealed that the diffusion process controlled the electrode reactions of all complexes and the free acid. The fluorescent properties of complexes 1³ and the ferrocenylacetate have been observed both in the solid state and in the solution state. The third-order nonlinear optical (NLO) properties of polymer 1 and 2 were also determined by Z-scan techniques.A novel coordination polymer 4 containing dimeric building blocks was prepared by the reaction of FcCH₂CH₂COONa with Zn(NO₃) -6H₂O under the help of 4,4'-bpy. In this...