Synthesis,Structure And Properties Of Multi-Hydrazide Coordination Complexes

In recent years,coordination supramolecular chemistry has welcome great development because of their fantastic structures,as well as their potential applications in molecular recognition,absorption/desorption,magnetic and optical feilds.For coordination supramolecular self-assembly,it is a key procedure to choose appropriate metal ions and ligands.In this context,three multi-hydrazide ligands were designed,synthesized,and characterized,N'2,N'2'-bis(2-hydroxybenzoyl)isophthalic dicarbohydrazide(H6L1),N'2,N'2'-bis(2-hydroxybenzoyl)biphenyl-2,2'-dicarbohydrazide(H6L2)and N'2,N'2'-bis(2-hydroxybenzoyl)thiophene-2,5-dicarbohydrazide(H6L3).The self-assembly of ligands(H6L1 and H6L2)and transitional metal ions was studied,generating a series of multi-hydrazide coordination compounds.The influences of ligand,metal ions and auxiliary agent on the self-assembly of coordination supramolecular were discussed based on structural analysis and properties characterization.The main work was summarized as follows.1.The combination of ligand H6L1 with copper ions leaded to compound 1 and 2,which were a pair of diastereoisomers,sharing the same molecular formula{Cu9(L1)3(C5H5N)6}n.The structural differences between two compounds were discussed,as well as the structural direction effect of ligand and the temperature influence.Magnetic measurement of compound 2 was taken and showed antiferromagnetic coupling effect at low temperature.2.The combination of ligand H6L2 with copper ions leaded to nine coordination compounds.{[Cu3L2(C5H5N)2]·DMF}n(3){[Cu3L2(DMF)(H2O)]·2DMF}n(4){[Cu3L2(DMA)(H2O)]·0.5DMA}2n(5){[Cu3L2(DMA)(H2O)]·DMF}n(6){[Cu3L2(DMF)2.5(C6H12N4)]·3H20}n(7){[Cu3L2(C4H9NO)(H20)]-DMA}n(8)[Cu3L2(C3H4N2)2]·2DMF(9)[Cu3L2(C3H4N2)2]·2DMA(10)[Cu6(L2)2(C3H4N2)2(DMA)2]·2DMA·2H20(11)These complexes all have[Cu3L2]coordination unit.With the mediation of diverse nitrogen-containing agents,the assembly of[Cu3L2]unit was various,with six 1D structures(compound 3?8),two 0D tri-nuclear structures(compound 9 and 10),one 0D hexa-nuclear structure(compound 11).The reported compounds were characterized by elemental analysis,X-ray powder diffraction,infrared spectrum,ultraviolet spectrum etc.Temperature-dependent of magnetic tests of compound 3 and 5 were taken to study the relationship of magnetic property and structure characteristics.3.The combination of ligand H6L2 with nickel ions leaded to compounds 12?15.Two are 0D structures(compound 12?13)and two are 1D structures(compound 14?15).[Ni3L2(DMA)4(C5H5N)4]·2DMA(12){[Ni3L2(DMF)(H20)]·1.5DMF·0.5H2O}2(13){[Ni3L2(DMF)2(H2O)2]·2DMF·1.2H2O}n(14){[Ni3L2(C4H9NO)2(DMF)]·DMF}n(15)Compound 12?15 share[Ni3L2]coordination unit in common,which is similar to[Cu3L2]in chapter four.The metal ions governed assembly behavior of[M3L2]unit was discussed by compared with compounds that harvested in chapter four.In addition,elemental analysis,X-ray powder diffraction,infrared spectrum,as well as ultraviolet spectrum of compound 12?15 were studied.