Study On The Synthesis And Properties Of Metal Complexes Containing Sulfonic Quinone Ligands

Because of unique redox characteristics,quinone compounds have many potential applications in such fields as energy storage,medicine,catalysis,molecular probe and so on.Coordination complexes based on quinone ligands may have similar applications,however,few studies have been done in this area,especially in relate to their physical and chemical properties.A systematic investigation on the generation and structure of transition metal and lanthanide complexes based on anionic ligand anthraquinone-1,8-disulfonate(Ll2-)is reported in this thesis.Fluorescent studies of these complexes reveal a potential fluorescence molecular switch and a promising candidate as fluorescence probe for Fe3+ion.The catalytic activities of some of the transition metal complexes ove selected organic reactions have also been studied.As an extention of this study,two other quinone ligands have been synthesized and their metal complexes are being studied.In chapter 2,a series of transition metal complexes based on L12' have been reported.Their structures were determined by X-ray single crystal diffraction,these complexes include[Cu(L1)(H2O)4]2(3),{[Mn(H2O)6]·[Mn(L1)2(H2O)2]}(4),{[Mn(L1)(H2O)2(CH3OH)]·(CH3OH}2(5),[Co(L1)(H2O)(CH3OH)3]·(CH3OH)(6),{[Co(L1)(H2O)2(CH3OH)]·(CH3OH)}2(7),[Ni(L1)(H2O)(CH3OH3]·(CH3OH)(8),[Ni(L1)(H2O)(CH3OH)3](9),[Zn(L1)(H2O)(CH3OH)3]·(CH3OH)(10),{[Zn(L1)(H2O)2(CH3OH)](CH3OH)}2(11),[Zn(L1)(H2O)3(CH3OH)](12),[Ag2(L1)(CH3OH]n(13),[Ag4(L1)2]n(14).Weak interactions such as hydrogen bonding and ?-? interactions exist widely in these complexes and contribute remarkably in the formation of 3D supramolecular structures.Through a detailed fluorescence study of the metal complexes,[Cu(L1)(H2O)4]2(3)is found to have different response in distinct pH range and is thus a potential pH sensitive fluorescence molecular switch.By systemetic investigations of the catalytic properties of these metal complexes over organic reaction,{[Mn(H2O)6]·[Mn(Ll)2(H2O)2]}(4)is found to be good heterogeneous catalyst over the oxidation reaction of diphenylacetylene toward benzil.Chaper 3 reports the synthesis and chacterization of a series of lanthanide complexes based on L12-,which include {[La2(L1)3(H2O)6]·(H2O)}n(15),{[Ce2(L1)3(H2O)6(CH3OH]·(CH3CH2OH}n(16),[Gd(L1)(H2O)5(NO3)]·(H2O)(17),[Sm(L1)(H2O)5(NO3)]·(H2O)(18).Similar as the cases of transition metal complexes,hydrogen bonding and ?-? interactions in these lanthanide complexrd also play important roles in the formation of 3D supramolecular structures.A systematic fluorescence study of the lanthanide complexes reveals that the Gd(?)complex has significant fluorescence enhancement in recongnizing Fe3+ ion in solution.Its fluorescence response of Fe3+ion is overwhelming compared to other metal ions and the co-existing of other metal ions together with Fe3+ion does not affect the fluorescence enhancement.Therefore,this complex is a good candidate as fluorescence probe for Fe3+ ion.Chapter 4 describes the syntheses of two new ligands as the extention of current study.Investigation of their coordination complexes and corresponding studies on their physical and chemical properties are underway.