二硫代草酸根桥联的双核镍(Ⅱ)配合物研究

Three binuclear Nickel(Ⅱ) complexes were synthesized, bridged with dithiooxalate, Ni₂(Bpy)₃(Dto)₂(H₂O)₃(1), Ni₂(Phen)₃(Dto)₂(H₂O)₃(2) and Ni₂(Me₂Bpy)₃(Dto)₂(H₂O)₂ (3) (Bpy=2,2′-Bipyridine, Phen=1,10-phenanthroline, Me₂Bpy=4,4′-dimethyl-2,2′-bipyridine, Dto^2-=Dithiooxalate), and characterized by elemental analyses, IR, UV-Visible spectra, conductance. The variable temperature magnetic susceptibilities for the complexes were measured in the range of temperature between 1.5 K and 298 K. Experimental data of magnetic susceptibility were successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=1, giving the magnetic exchange parameters of 2J=-52.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions. The magnetic exchange parameters of the binuclear Nickel(Ⅱ) complexes bridged with dithiooxalate is larger than that of the binuclear Nickel(Ⅱ) complexes bridged with oxalate. Dithiooxalate is more effective to transfer antiferromagnetic spin exchange interaction between the Ni(Ⅱ) ions than oxalate.     

μ-邻苯二甲酸希土与5-硝基-1,10-菲咯啉双核配合物的合成、光谱、磁性

本文合成了四个以邻苯二甲酸阴离子为桥联配体的新型希土双核配合物［Ｌｎ２（Ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４．ｘＨ２Ｏ［Ｌｎ＝Ｇｄ，Ｈｏ，Ｅｒ，ＮＯ２－Ｐｈｅｎ＝５－硝基－１，１０－菲咯啉，Ｐｈｔｈ－邻苯二甲酸阴离子）。经元素分析，ＩＲ，电导，电子吸收光谱，表征了配合物，测定了［Ｇｄ２（ｐｈｔｈ）（ＮＯ２－ｐｈｅｎ）４］（ＣｌＯ４）４．４Ｈ２Ｏ的变温磁化率（４－３００Ｋ），其数值用最小     

Exchange Interaction of a Novel Heterospin Polynuclear Complex Containing Transition Metals and Imino Nitroxide Radicals: {[(CuL)Ni(IM-2Py)_2](ClO_4)_2}_2·2H_2O

IntroductionThemajorresearchaimsinthefieldofmolecularmag netismareontheonehandthedesignofmolecularassembliesthatexhibitaspontaneousmagnetizationandontheotherhandtherationalizationofmagnetostructuralcorrelation .1Polynuclearmacrocycliccomplexesandnitroxideradicalmetalliccomplexesaretwoactivefieldsofresearchfordesign ingandsynthesizingnewmagneticmaterials.2 6Polynuclearmacrocycliccomplexescontainingmul tiatomicbridgesuchasphenolateoxygen ,oxamidoandoxi amtogroupshavebeenconsiderablyinvestigated…     

2, 6─二甲酸─4─取代苯酚双缩苯甲酰肼双核铜(Ⅱ)配合物的合成与磁性

本文合成并表征了两个新的双核铜（Ⅱ）配合物：［Ｃｕ２（Ｌ）（μ－Ｃｌ）Ｃｌ２］，配体Ｌ为２，６－二甲酰－４－基苯酚双缩苯甲酰肼，取代基分别为氯（Ｌ１）和叔丁基（Ｌ２）。配合物具有相同的组成和配位构型。变温磁化率测定结果表明，由于取代基不同，其磁交换参数分别为－４６．２ｃｍ＾－１（Ｌ１）和－５７．６ｃｍ＾－１（Ｌ２）。     

二(μ-叠氮)二[N,N'-二(2-吡啶甲基)乙二胺]合二镍(Ⅱ)配 合物的结构与磁性

合成并通过元素分析、红外光谱、电子光谱等方法表征了叠氮桥联的双核配合物[Ni2(bispicen)2(μ-N3)2](ClO4)2[bispicen=N,N'-二(2-吡啶甲基)乙二胺].用单晶X射线衍射技术测定了配合物的晶体结构,晶体属正交晶系,P212121空间群,镍(Ⅱ)离子处于变形八面体配位环境,并采取cis-α构型,两个以μ-1,3桥联方式配位的叠氮离子之间呈罕见的交错式非平面排列。变温磁化率测定表明配合物两个镍(Ⅱ)离子之间存在反铁磁相互作用,基于H^=-2JS1^S2^的磁性分析表明磁交换积分J=-28.1cm^-1。     

四核Mn(Ⅳ)配合物[L_4Mn_4O_6](ClO_4)_4·2H_2O的合成、结构及磁性研究

近年来 ,由于在金属蛋白中发现氧桥联锰配合物的结构单元[1～ 3] ,对这类配合物的研究更加受到人们的重视 .多核锰配合物的化学研究也随着新型无机材料的发展而引起人们更大的兴趣 [4 ] .本文以大环配体 tacn(即 1 ,4,7-三氮杂环壬烷 )为端基配体 ,合成了四核 Mn( )配合物 [L4 Mn4 O6]( Cl O4 ) 4 ·2 H2 O,并对其结构及性质进行了研究 .1　配合物的合成将 0 .1 2 9g( 1 mmol) tacn[5,6]配体溶于 2 0 m L甲醇中 ,加入到 0 .2 4 5 g( 1 mmol) Mn( CH3COO) 2 ·4H2 O的 1 0 m L水溶液中 ,于室温下搅拌 5 h后得到深蓝色溶液 .再加入 0…     

From Dinuclear to Mononuclear：Co（Ⅱ） Complexes with Pyridine-2,6-Dicarboxylic Acid（H_2PDA）

Reactions of pyridine-2,6-dicarboxylic acid(H2PDA) with cobalt(Ⅱ) acetate resul-ted in two cobalt(Ⅱ) complexes,[Co(HPDA)2].2H2O.0.5CH3OH(1) and [Co2(PDA)2(H2O)5].2H2O(2),which were characterized by single-crystal X-ray diffraction,IR and electronic absorption spectra.For both complexes,every cobalt atom lies in peudo-octahedral coordination geometry,and the whole structures present 3D frameworks linked by π-π stacking interactions and extensive hydrogen bonds.Magnetic studies showed λ =-83.38 cm-1 for(1) and g = 2.50 and J =-1.38 cm-1 for(2).     

联苯-2，2′-二甲酸-2-甲酯的合成、结构及表征

最新的药理活性试验表明，具有联苯结构单元的化合物对于肝癌的标记物甲胎蛋白(AFP)及人免疫病毒(HIV)有一定的作用．在金属催化和新型磁性材料合成方面，化学家对以联苯二甲酸类物质桥联的配合物已进行了广泛研究。