N,N′-双(2-氨基丙基).草酰胺合铜(Ⅱ)的铜(Ⅱ)-锰Ⅱ配合物的合成和磁性

合成和表征了两种新的异双核配合物[Cu(oxap)Mn(L)_2](ClO_4)_2,oxap表示N,N'-双(2-氨基丙基)草酰胺根阴离子,L表示1,10-邻菲喀啉(phen)和5-硝基-1,10-邻菲咯啉(NO_2-phen)。测定了配合物的变温磁化率(4.2—300K),并用最小二乘法和从自旋Hamiltonian算符,=-2JS_1·S_2-DS_(s1)导出的磁方程拟合,求得交换积分为J=-74.72cm~(-1)(phen)和J=-76.39cm~(-1)(NO_2—phen),表明两个Cu(Ⅱ)-Mn(Ⅱ)双核配合物中有中等强度的反铁磁超交换作用。     

一个包含Cu（Ⅱ）和氮氧自由基自旋支链的新颖杂自旋一维链状化合物的结构和磁性研究

本文合成了一个含Cu（Ⅱ）离子和氮氧自由基自旋支链的新颖杂自旋-维链状化合物{[Cu（tcph）（H20）4][cu（tcph）（NIT3Py）2]·2H2O}n（1）（tcph=四氯令K苯二甲酸,NIT3Py=2．（3’-吡啶基）-4,4,5,5-四甲基咪唑啉-3-氧化-1-氧基自由基）．对其结构分析表明,该配合物是一个由四氯邻苯二甲酸连接Cu（Ⅱ）离子构成的一维链状化合物,其中自由基作为自旋支链与水分子分别交替与链上的Cu（Ⅱ）离子进行配位．磁性研究中我们采用了计入自旋态布居的一维链近似模型对其磁性数据进行了合理的拟合,得到以下耦合参数：Jcu2-Rad=22．4cm^-1和J′cul-cu2=-2．4cm^-1,表明分子内Cu2与NIT3Py自由基问存在铁磁相互作用,而由四氯邻苯二甲酸连接的Cu1和Cu2间存在反铁磁作用．     

Crystal Structure of a Copper(II) Complex with 2,3-Dioxo-5,6:13,14-dibenzo-9-methyl-7,12- bis(ethoxycarbonyl)-1,4,8,11- tetraazacyclotetradeca-7,11-diene

1 INTRODUCTIONThe coordination chemistry of macrocyclic compounds has received considerable attention for several decades, primarily due to its importance in biological processes[1]. A variety of 12 ~ 15 membered polyamine and polyoxotetraaza macrocycles have been found to be especially effective in stabilizing oxidation states of the complexed metal ion that are inaccessible for complexes with noncyclic ligands[2~5]. Very recently, we demonstrated that a series of macrocyclic oxamido Sch…     

普鲁士蓝类分子磁体研究的新进展

在分子磁体的研制中,多氰金属盐是一类非常合适的分子前体。它有可能组装成高自旋基态、高居里温度或具有各向异性的分子基磁体。本文将介绍此类分子磁体的研究新成果及发展前景。     

三维氢键超分子化合物[H3cth][Fe(CN)6]·3H2O的合成与结构

用内消旋５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四烷（ｃｔｈ）和Ｋ_３［Ｆｅ（ＣＮ）_６〕合成了氢键连接的超分子化合物［Ｈ_３ｃｔｈ］［Ｆｅ（ＣＮ）_３］·３Ｈ_２Ｏ．该化合物的晶体属三斜晶系，Ｐ－１空间群，晶胞参数ａ＝０．９３０ ９７（９）ｎｍ，ｂ＝１．０５１ ６０（１１）ｎｍ，ｃ＝１．６３８ ４７（１７）ｎｍ，ａ＝１０１．０７７（２）°，β＝９０．８６０（２）°，γ＝１１１．６７１（２）°， Ｖ＝１．４５６ ４（３） ｎｍ３， Ｚ＝２， Ｒ＝０．０４１５．晶体中质子化的大环四胺与六氰合铁（Ⅱ ）离子之间通过氢键连接成二维层状结构，而水分子所形成的氢键使化合物呈现三维超分子网络．     

Synthesis and Uncommon Structural Characterization of Novel Zinc and Cadmium Complexes with Imino Nitroxide Radical

Two novel complexes {[Zn(IM4py)2(tp)(H2O)]·2H2O}n 1 and {[Cd(IM4py)2(tp)- (H2O)]·1.25H2O}n 2 (IM4py = 2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and tp = terephthalate dianion) have been synthesized and characterized by elemental analyses, IR spectrum and single-crystal X-ray diffraction. Crystal data for complex 1: monoclinic, space group C2/c, a = 20.648(7), b = 12.130(4), c = 14.036(4) , β = 106.351(5)o, C32H42N6O9Zn, Mr = 720.09, V = 3373.3(2) 3, Z = 4, Dc = 1.418 g/cm3, μ(MoKα) = 0.790 mm-1, F(000) = 1512, the final R = 0.0407 and wR = 0.0894 for 3480 independent reflections with Rint = 0.0432. Crystal data for complex 2: monoclinic, space group C2/c, a = 21.332(6), b = 12.063(3), c = 14.246(4) , β = 106.704(4)o, C32H40.50N6O8.25Cd, Mr = 753.60, V = 3511.2(2) 3, Z = 4, Dc = 1.426 g/cm3, μ(MoKα) = 0.679 mm-1, F(000) = 1554, the final R = 0.0419 and wR = 0.0961 for 3627 independent reflections with Rint = 0.0440. The framework structures of complexes 1 and 2 are 3-D networks via the hydrogen bonds among 1-D chains. The notable characteristics of the two complexes are that the coordination polyhedron of Zn(II) adopts a rare distorted five-coordinate square pyramidal geometry in 1, and the Cd(II) complex exhibits an unusual distorted seven-coordinate pentagonal bipyramid in 2.     

Synthesis, characterization and magnetic properties of μ-iodanilato dinuclear oxovanadium (Ⅳ) complexes

Five oxovanadium(Ⅳ) dinuclear complexes described by the overall formula [(VO)2(IA)L2]-SO4, where IA represents the dianion of iodanilic acid and L denotes 2,2'-bipyridine (bpy) ; 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 1,10-phenanthroline (phen); 4,7-diphenyl-1, 10-phenanthroline (Ph2-phen) and 5-nitro-l, 10-phenanthroline (NO2-phen) , have been synthesized and characterized by elemental analyses, molar conductivity and room-temperature magnetic moment measurements, IR and electronic spectral studies. It is proposed that these complexes have IA-bridged structures and consist of two oxovanadium(Ⅳ) ions each in a square- pyramidal environment. The complexes [ ( VO)2 (IA) (bpy )2 ] SO4 (1) and [ ( VO )2 ( IA) ( phen)2 ] -SO4 (2) were further characterized by variable temperature (4.2-300 K) magnetic susceptibility measurements and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method, giving the exchange integral J = -2.15 cm-1 for 1 and J = - 9.88 cm-1 for 2     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(Ⅲ) complexes

Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.     

含氮配体过渡金属络正离子与[Ni(cdc)2]2-加合物的电子光谱和电导率研究

研究了10个含氮配体的过渡金属络正离子与[Ni(cdc)2]2-加合物在溶液和固体状态下的电子光谱和溶液电导率,发现电导率(Ω-1·cm2·mol-1)和加合物在Ha介质中π-π*跃迁带vmax(cm-1)值呈一致的变化关系.对吸收峰作出了归属,指定了负离子的MLCT带,并指出极性溶剂使MLCT带蓝移,π-π*跃迁带红移.