Studies On Metal Complexes Of Dihydrazone Ligand Bearing Indane-1,2,3-trione-1,2-di(3-Methoxysalicyhydrazide) Hydrazone

Bisacylhydrazone compounds are one kind of Schiff bases formed by the condensation reaction of diacylhydrazine with aldehyde/ketone or hydrazine with dialdehyde/diketone,which are often selected as ligands to react with metal ions to form complexes for they showing various coordination modes and different bonding characteristics,due to they have strong coordinating atoms of nitrogen and oxygen.In this thesis we focus our attention on the synthesis of multicarbonyl Indane-1,2,3-trione with multi-coordination sites salicylhydrazide.The effect of the rigidity and flexibility,the location of the coordination sites of the ligand and the coordination environments of metal ions on the construction and the architectures of the complexes will be inverstigated.For this purpose,a multidentate ligand,Indane-1,2,3-trione-1,2-di(3-methoxysalicyhydrazide)hydrazone(H4L)was prepared,and new 10 coordination compounds(polymers)ware obtained by the reactions of the ligand with transition metal ions.They were characterized by elemental analysis,infrared spectroscopy,powder X-ray diffractional analysis and single crystal X-ray diffractional analysis.The luminescent and magnetic properties of some coordination compounds were studied.1.The reactions of the ligand with transition metal salts in different solvents gave four metal compounds:[Ni(H2L)]·(C2H5)3N·CH3OH(1),[Co(H2L)(Py)2]·CH3OH·H2O(2),Mn(H2L)(CH3OH)2(3),and[Cu2(L)(H20)(Py)]-H2O-CH3CN(4).They were determined by single-crystal X-ray diffraction analysis and elemental analysis,IR spectra.In compound 1,Ni(?)ion is four-coordinated in a distorted tetrahedron geometry,in compound 2 and 3,metal ions are six-coordinated in a distorted octahedral geometry,in compoud 4,one of Cu(?)ions is four-coordinated in a distorted tetrahedron geometry and another is five-coordinated quadrangular pyramid geometry.The luminescent properties of compound 1 and 3 was studied.The low-temperature solvothermal reactions of H4L with MnCl2-H2O or MnCl2-H2O/DyCl3·6H2O in different solvents gave two polynuclear manganese(?)clusters[Mn6(L1)2(L2)2(mdea)2Cl2](5)and[Dy2Mn2(L1)4(L2)2](6).They crystallize in the Moniclinic P21/c group with a=10.4156(3)(?),b=22.4659(6)(?),c=29.5584(10)(?),p=99.941(2)° in clustet 5,and a=16.454(9)(?),b=11.648(7)(?),c=21.684(12)(?),?=102.345(9)° in cluster 6.The H4L was broked up into two parts L1 and L2 in the reaction process.The core topology of cluster 5 and 6 are a defect-cubane motif.Compound 6 was heter-metallic cluster composed by manganese and dysprosium.The manganese ions are seven-coordinated in a distorted single-cap octahedral geometry,while the dysprosium ions are eight-coordinated distorted square antiprismatic geometry.Magnetic measurement revealed the presence of antiferromagnetic coupling in cluster 5 and 6.Alternating current susceptibility data indicated that cluster 5 and 6 show single-molecule magnetism behavior.3.A centrosymmetric hexanuclear copper cluster[Cu6(L")2Py14]·2(ClO4)2-3CH3OH-H2O has been synthesized by slowly evaporating solvent at room temperature.The complex has been characterized by single-crystal X-ray diffraction,which shown that the complex belongs to triclinic,space group P-1 with a=13.9034(12)(?),b=14.0752(12)(?),c=18.1584(16)(?).The low-temperature solvothermal reactions of H4L with CuX2(X=Cl/Br/I)in different solvents gave three polynuclear Cu2?Cu6?(L')2(thma)2Cl2(8),[Cu2?Cu6?(L')2(thma)2Br2(CH3OH)2]n(9)and[Cu2?Cu6?(L')2(thma)2I2(H2O)2]n(10).Compound 8 crystallize in the orthorhombic Pbca group with a=21.076(7)(?),b=13.773(5)(?),c=22.122(7)A.Compound 9 crystallize in the Moniclinic P21/c group with a=11.4674(5)(?),b=19.287(1)(?),c=16.2231(6)(?),?=109.823(5)°.The ligand H4L has decomposed in the reactions with Cu salts.The complex 8 is a mixed-valence ?Cui} cluster which present the double-layer structure.Complex 9/10 presents octanuclear units [Cu 2?Cu6? 6(L')2(thma)2Br2(CH3OH)2]/[Cu2?Cu6?(L')2(thma)2I2(H2O)2]as repeating units,which are bridged by[Cu2?Br2]/[Cu?2?2]subunit to form one-dimensional step.