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.