Studies On Metal Complexes Of Dihydrazide Ligands Based On N,O-heterocycles Dicarboxylic Acid

Hydrazide compounds are one kind of organics formed by substitution reaction of hydrazides or derivatives with esters or acyl-chlorides,which are often selected as ligands to react with metal ions to form complexes with novel structure and unique property for they show strong coordinating abilities of N?O and a variety of coordination modes.The pyridine dicarboxylic acid and furan dicarboxylic acid ligands for containing heteroatoms on their rings,enhance the ligand coordinating abilities,fully embody the chemical activity of this kind of ligand,and forming complexes have received extensive attention of the researchers.In this thesis,five complexes(1-5)were prepared from ligands of 2,6-pyridine-diacylhydrazide by routine solution methods and low-temperature solvothermal methods.Two complexes(6-7)were prepared from ligands of 2,6-pyridine-dipicolinylhydrazide by solvothermal method.Two complexes(8-9)were prepared from ligands of 2,5-furan-diacylhydrazide by solvothermal method.They were characterized by elemental analysis,infrared spectroscopy,single crystal X-ray diffractional analysis,powder X-ray diffractional analysis.We also systematic studied their structures and properties.The reaction of the ligand of 2,6-pyridine-diacylhydrazide gave five clusters:[Mn?Mn?2(pdshz)(acac)2(CH3OH)4](1);[Mn?Mn?2(pdshz)(acac)2(CH3OH)2(Py)2]�3CH3OH(2);[Mn?Mn ?2(pdshz)(acac)2(Py)4]�2Py(3):[Co ? Co ?2(pdshz)(Py)8]2+�(ClO4)2�2Py(4);[Cu6(pdshz)2(Py)4](5).The sinlge crystal X-ray diffractional analysis results revealed that compound(1)crystallized in the orthorhombic space groupPbcn with a = 17.0744(3)A,b =20.5494(4)A,c =11.4918(2)A.Compound(2)crystallized in the monoclinic space group C2/c with a = 21.674(9)A,b = 15.5645(17)A,c = 28.359(4)A.Compound(3)crystallized in the orthorhombic space groupPbcn with a = 16.223(6)A,b=20.233 A,c = 20.233(7)A.Compound(3)crystallized in the triclinic space group Pi with a= 10.3677(16)A,b = 11.2693(17)A,c = 28.801(4)A.Compound(3)crystallized in the triclinic space group Pi with a =11.9690(6)A,b = 14.4468(6)A,c = 17.6248(9)A.Complexes(1-4)contain a ligand and three metal irons to form linear clusters.The magnetic properties of complexes were studied.It reveals that complexes(1-3)present ferromagnetic interactions between Mn ions and complex(5)presents antiferromagnetic interactions between Cu ions.The reaction of the ligand of 2,6-pyridine-dipicolinylhydrazide gave two clusters:[Mn?9Mn ? 4(pdpdhz)5(?2-O)2(?-O)3(H2O)3]�2DMF(6)and[Co ? 8Co ? 3(pdpdhz)5(?3-O)2(HCOO)3(H2O)4](7).The sinlge crystal X-ray diffractional analysis results revealed that compound(6)crystallized in the monoclinic space group P21/c with a=15.6159(12)A,b=34.788(3)A,c = 21.5256(1 7)A.Copound(7)crystallized in the monoclinic space group P21/c with a = 16.0324(8)A,b = 33.881(8)A,c = 21.1565(10)A.Comolexes(6)contains five ligands and thirteen metal irons and Complexes(7)contains five ligands and eleven metal irons,they are both similar to the butter-fly shape.The thermogravimetric analysis of complexes were studied.The reaction of the ligand of 2,5-furan-diacylhydrazide gave two clusters:[Co?3Co?2(H2frshz)2Py6(?2-O)2]n�2Py�CH3CH2OH�H2O(8)and[Ni6(frshz)2Py5]�Py(9).The sinlge crystal X-ray diffractional analysis results revealed that compound(8)crystallized in the tetragonal space group P42/n with a = 17.5753(11)A,b = 17.5753(11)A,c = 27.826(2)A.Compound(9)crystallized in the triclinic space group Pi with a = 10.6245(4)A,b = 15.6459(6)A,c = 20.5317(7)A.Complex(8)presents pentanuclear units[Co ? 3Co?2(H2frshz)2Py6(?2-O)2]as repeat units,which are bridged by oxygen atom to form one-dimensional chain structure.Through the two Ni connects two ligands with the coordination mode of ?4-?3:?2:?2:?3,Complex(9)eventually forms Ni6 clusters.The thermogravimetric analysis of complexes were studied.