Studies On The Structure And Bioactivity Of Ferrocene-containing Complexes

Ferrocene and its derivatives have been extensively applied in to chemical matterals due to their unusual structure and their special properties of opticals, electronics, magnetic and catalysts et al. They also attract much attention in medical field for their low toxicity. In this dissertation, the studies on the bioactivity of the ferrocene and its derivativeshave been reviewed in detail, and a series of new complexes were synthesized by use of ferrocenecarboxylic acid and N-ferrocenylformylglycine . The complexes have been characterized by IR,elemental analysis and crystal X-ray diffraction ,and the bioactivity of complexes were studied also. Main work is listed as following:1. Four zinc complexes, whose molecular structure formulas are [(FcCOO-)(phen)2Zn(II)]+ ClO₄^-·FcCOOH(1)(FcCOO^-=ferrocenecarboxylate,phen=1,10-phenanth-roline,FcCOOH= ferrocenecarboxylic acid), [FcCOO-)(phen)₂Zn(II)]+·ClO₄^-·H₂O(2), [(FcCOO^-) (FcCOGly^-) (phen)Zn(II)]·C₂H5OH(3)( FcCOGly= N-ferrocenylformylglycine) and [(FcCOGly-)2(phen) Zn(II)]·CH₃OH(4) separately, were synthesed by use of ferrocenecarboxylic acid and N-ferrocenylformylglycine and assistant ligand 1, 10-phenanthroline.The complex(1) and complex(2) are belong to monoclinic crystal system . The complex(1) belong toP2(1)/n space group and with cell parameters a = 9.6338(17)·,b = 15.037(2)·,c = 27.604(3)·,α= 90°,β= 95.210(2)°γ= 90°; The complex(2) belong toP2(1)/c space group and with cell parameters a = 15.919(2) A,b = 21.285(2) A,c = 23.835(3) A,α= 90°,β= 127.560(3)°,γ= 90°;Complex (3) crystallizes in the triclinic space group P-1 with a = 11.686(3) A,b = 12.897(3) A,c = 13.843(3) A,α= 66.341(2)°,β= 68.526°,γ= 65.021°。Complex (4) crystallizes in the Orthorhombic space group Aba2 with a = 20.727(3)·,b = 19.689(3) A,c = 9.885(2) A,α= 90°,β= 90°,γ= 90°.The ferrocenecarboxylate and N-ferrocenylformylglycine of those complexes are all coordinate with zinc by single oxygen atom, except complex(2) who has theη2-FcCOO-. By studying on their molecular structure and activity, we found that the antibacterial activity of those complexes related with their stability in a large extent. Complex (1),(2),(3) possess good antibacterial activity , that is, for some bacterias, even if their concentration only one twentieth of Gentamycin's, the diameter of inhabit bacterial are near to the Gentamycin's. 2.Two ferrocenecarboxylic acid ligand rare earth complexes ,[Pr(III)2 (μ²-η²-OOCFc) 2 (OOCFc)₄ (H₂O)₄]·CH₃OH·H₂O(5)and [Dy(III)2 (μ²-η²-OOCFc) 2 (OOCFc)₄ (H₂O)₄]·CH₃OH·H₂O(6) ,were synthesed. and Complex (6) crystallizes in the triclinic space group P-1 with a similar cell parameters.Complex (5) with a = 8.923(2) A,b = 14.539(3) A, c = 15.367(3) A,α= 117.501(3)°,β= 105.422(2)°,γ= 91.046(2)°and complex (6) with a = 8.811(2) A,b = 14.485(3) A,c = 15.267(4) A,α= 117.194(3)°,β= 105.266(2)°,γ= 90.903(3)°。The rare earth atoms coordinate with nine oxygen atoms. Two of ferrocenecarboxylates coordination in the mode ofμ²-η2-FcCOO-,which bridge two rare earth atoms to dimeric cores structure.The other four ferrocenecarboxylates coordination in the mode ofη²-FcCOO- .Comparing to the ligand and inorganic aslt ,the bioactivity of complexes changed in a large scale. 3.A trinuclear zinc(II) complex with ferrocenecarboxylates, [Zn(II)3(μ²-CH3COO-)2(Fc COO-)4(phen)2](7),was synthesed. Its crystallizes in the triclinic space group P-1 with a=10.936(2)A, b=11.360(2) A, c = 13.915(3) A,α= 68.852(2)°,β= 82.279(3)°,γ= 85.925(3)°. The complex molecule has a centrosymmetric structure, and three zinc atoms are in one line. The coordination of each ferrocenecarboxylate in the mode ofμ²-η²-FcCOO-, while the acetate in the mode ofμ²-CH3COO-.By the study on the fluorescent property of complex(7), it is found that ,comparing with the ferrocenecarboxylic acid ,the fluorescence of complex(7) is stronger.