| In the context of energy and environmental crisis,the development of such fields as heterogeneous catalysis and fluorescence sensing is becoming more and more important.With the development of coordination chemistry,various potential applications of coordination complexes have received extensive attention.Their poor solubility in non-aqueous solvents makes them good candidate for heterogeneous catalysts.Their optical properties also dictate potential applications as fluorescent probes.The functional design and synthesis of coordination complexes is key for its application studies.The functionalization of metal complexes can be achieved by ligand functionalization or selection of metal ions/clusters.Based on the characteristic photosensitivity of quinone compounds,anthraquinone was selected as basic building unit of the ligand and 3,7-diamino-9,10-anthraquinone-2,6-disulfonic acid(L1)and its metal complexes have been thus synthesized.Further studies of their performance as photocatalysts to catalyze organic small molecule reactions and as fluorescent ion probes proved that some of the lanthanide complexes based on L1 are excellent photocatalysts and fluorescent probe.Prospective exploration of some other functional ligands have also been carried out,and a few new ligands have been synthesized,which include 1,5-diamino-9,10-anthraquinone-2,6-disulfonic acid(L2),2,7-dipyridyl-9,10-phenanthrenequinone(L3)and 2,4,7-trisulfonic acid-9,10-phenanthrenequinone(L4).Preliminary synthesis of metal complexes of L2 has also been carried out.The thesis constitutes five chapters as follows:In chapter 1,the development of coordination chemistry and coordination compounds,the studies realted to sulfonate ligand-based coordination complexes,the research progress of metal complexes based on quinone ligands,and the studies of coordination compounds in the field of photocatalysis have been briefly reviewed.In chapter 2,the ligand 3,7-diamino-9,10-anthraquinone-2,6-disulfonic acid(L1)was designed and synthesized,which was characterized by means of NMR,IR and X-ray single crystal diffraction.Then 14 metal complexes of ligand L1 were synthesized,which were characterized by X-ray single crystal diffraction,X-ray powder diffraction,IR,fluorescence spectroscopy,UV-vis spectroscopy,elemental analysis,and thermogravimetric analysis.Structural analysis indicates that complexes[La2(L1)2.5(H2O)15]·0.5L1·10H2O(1),[Nd2(L1)2.5(H2O)15]·0.5L1·12H2O(2),[Sm2(L1)2(H2O)15]·L1·4H2O(3),[Eu2(L1)2(H2O)15]·L1·4H2O(4),[Dy(L1)1.5(H2O)6]·[Dy(H2O)8]·1.5L1(5),[Ho(L1)1.5(H2O)6]·[Ho(H2O)8]·1.5L1·8H2O(6),[Er(L1)(H2O)6]·[Er(H2O)8]·2L1·8H2O(7),[Tm(L1)(H2O)6]·[Tm(H2O)8]·2L1·8.5H2O(8),[Yb(L1)(H2O)6]·[Yb(H2O)8]·2L1·9H2O(9),[Lu(L1)(H2O)6]·[Lu(H2O)8]·2L1·9H2O(10),[Cu(L1)0.5(H2O)5]·0.5L1·3H2O(11),[Cu2(L1)(DMF)8]·L1(12),and[Cu(L1)(DMF)4]·2DMF(13)have discrete coordination unit in their crystal structures,while{[Zn0.5(L1)0.5(DMF)2]·(DMF)}n(14)has one-dimensional chains.Versatile hydrogen bonding and?-?stacking interactions exist in the crystal structure of these complexes,which play important roles in stabilizing the three-dimensional packing of the crystals.In chapter 3,the photocatalytic performance and fluorescence properties of some lanthanide metal complexes based on L1 ligands are studied.The results show that these lanthanide metal complexes are good heterogeneous photocatalysts,which can be used to catalyze the conversion of diarylacetylene into 1,2-diketone,and sulfide into sulfoxide in the photooxidation reaction.Complex 7 shows the best catalytic efficiency over a wide range of substrate scope for both types of reactions,with the highest yields being 72%and 86%,respectively.The catalyst can be separated by simple filtration after the completion of the photooxidation reactions and X-ray powder diffraction reveals no structural change.The catalyst can be recycled for at least five catalytic cycles without loss of efficiency.On the other hand,the fluorescence properties of several other lanthanide metal complexes based on L1ligands were also systematically studied.The results show that they are excellent“turn-on”fluorescent probes for Fe3+ion,with good selectivity and good anti-interference performance for common metal ions.In chaper 4,the prospective exploration of the design and synthesis of a few new functional ligands were carried out,which include 1,5-diamino-9,10-anthraquinone-2,6-disulfonic acid(L2),2,7-dipyridine-9,10-phenanthrenequinone(L3)and2,4,7-trisulfonic acid-9,10-phenanthrenequinone(L4).They were characterized by NMR,IR and X-ray single crystal diffraction.One transition metal complex of ligand L2 was synthesized.Further exploration of the coordination chemistry of these ligands,together with the investigation of their properties are underway.In chapter 5,conclusion remarks and prospectives are given. |
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