1，4-二氮杂二环[2.2.2]辛烷-1，4-二乙酸配合物的合成、结构与磁性

合成了{[M(L)₂(H₂O)₂](ClO₄)₂·4H₂O}_n(M=Cu 1,Co 2;L=1,4-二氮杂二环[2.2.2]辛烷-1,4-二乙酸),并进行了元素分析、红外、热重、变温磁化率等表征。单晶结构表明这2个配合物属于单斜晶系,P2₁/c空间群。Cu(Ⅱ)和     

磷酸酯桥联和端基配位的双核铁(Ⅲ)配合物

为了模拟氧化型紫色酸性磷酸酶的活性中心 ,合成出一个分子式为 [Fe2 (HPTB) {μ O2 P(OPh) 2 }{O2 P(OPh) 2 }2 ](ClO4) 2 ,(HPTB =N ,N ,N′,N′ 四双 ( 2 苯并咪唑甲基 ) 2 羟基 1 ,3 二胺丙烷 )的双核铁的配合物 .晶体结构分析表明 ,配合物分子中双核铁 (Ⅲ )被一个来自配体的烷氧基和一个双齿配位的磷酸二苯酯桥联 ,同时2个单齿配位的磷酸二苯酯分别与一个铁离子配位 .2个铁离子均为六配位的畸变八面体几何构型 .晶体学数据 :三斜晶系 ,P1空间群 ,a =1 .5 1 2 1 3( 5 )nm ,b =1 5 91 1 9( 5 )nm ,c =1 .890 90 ( 5 )nm .α =6 9.92 5 ( 1 )° ,β =84.35 8( 1 )° ,γ =6 5 .71 2 ( 1 )°,Z =2 .研究了配合物的电子吸收光谱 ,1HNMR和磁性     

从“路边苦李”到“反证法”

有一则小学生读物中的推理故事《路边苦李》,其文言表述如下: 王戎七岁,尝与诸儿游,看道边李树多子折枝,诸儿竞走取之,唯戎不动.人问之.答日:“树在道边而多子,此必苦李”.取之,信然.     

Exogenous bridge and tautomer effects on magnetic interaction of binuclear copper(II) complexes of μ-phenolato Schiff bases

Four enol-form binuclear copper complexes with different exogenous bridges, [Cu2(L)(μ-Cl)] (1), [Cu(L)(μ-N3)]· DMF (2), [Cu2(L)(μ-OCH3)] (3) and [Cu2(L)(μ-C3H3N2)]· 1/2C2H5OH (4), where L is the trivalence anion of binucleating ligand 2,6-diformyl-4-methylphenol di(tenzoylhydrazone), have been synthesized and characterized. Crystal data for complex (3) are as follows: space group P1- , a=0.8294(1), 6=0.9333(3), c= 1.473 6(6) nm, α=79.51(3)°, β=80.93(2)°,γ=81.32(2)°, Z=1. The magnetic measurements indicated that the effect of exogenous bridging ligands on magnetic interaction is corresponding to that in spectrochemical series. The effect of enol- and keto-form tautomer on magnetic interaction was explained from the point of view of structural factors and electron effects by using molecular mechanks and quantum chemistry calculations.     

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.     

N,N'-双(2-吡啶乙基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及性质

0引言多原子桥联配体的多核配合物中,顺磁离子间磁偶合作用的研究对阐明磁性和结构的关系以及设计新型分子基磁性材料具有重要的理论意义。草酸根及草酰胺根桥联的多核配合物得到了较为广泛和深入的研究[1~5]。硫原子取代两个氧原子后,形成二硫代草酸根及二硫代草酰胺根,由于硫     

氰根桥连的锰钴五核配合物的合成与晶体结构

Reaction of [Mn(bpm)₂]²⁺ with K₃[Co(CN)₅(NO)] produces a cyano-bridged bimetallic compound,{[Mn(bpm)₂]_1.5[Co(CN)₅(NO)]}·2H₂O (1), (bpm=bis(1-pyrazol)methane). Compound 1 crystallizes in the tetragonal space group P4₃2₁2 with a=1.305 08(8) nm, b=1.305 08(8) nm, c=4.386 7(5) nm, V=7.471 5(10) nm³, and Z=8. Complex 1 exhibited a structure of a pentanuclear cluster. The Mn²⁺ ions each are surrounded by bpm ligands, forming the [Mn(bpm)₂]²⁺ cation fragment. Three cation fragments are connected to the two anion fragments, [Co(CN)₅(NO)]^3-, by cyanide bridges. The five metal ions form a trigonal bipyramidal structure, where the Mn²⁺ ions are situated in the equatorial plane and the Co²⁺ ions are on both sides of the plane. As a semirigid ligand, bpm is more flexible than rigid 2,2′-bipydine, and it results in the two different configurations in the [Mn(bpm)₂]²⁺ cation fragment. CCDC: 635764.     

对化学的挑战——分子铁磁体的设计

寻求常温下的分子铁磁体是自然界向化学家挑战的一个热点课题.本文介绍了迄今美、俄、法、日等国家在该领域已取得的最新成果及已采用的几种设计与合成途径,即有机方法、金属有机方法、金属—自由基方法和无机方法等.其中通过无机方法制得的铜锰交替链状配合物的铁磁相转变温度(T_c)达到30K,这是目前通过各种方法制得的T_c最高的分子铁磁体。     

乙酸根与1，6-二(1H-1，2，4-三唑)己烷交替桥联的一维Cu(Ⅱ)配位聚合物

Using a new ligand 1,6-bis(1,2,4-triazole-1-yl)hexane (L), one-dimensional coordination polymer [Cu₂(L)(CH₃CO₂)₄]_n has been synthesized and characterized by elemental analysis, FTIR spectra and X-ray single crystal structural analysis. The title complex crystallizes in triclinic system with space group P1, a=0.722 5(7) nm, b=0.808 0(8) nm, c=1.173 1(11) nm, α=72.294(11)°, β=88.049(11)°, γ=66.294(11)°, V=0.594 2(10) nm³, Z=1, R₁=0.037 0, wR₂=0.098 3. The fundamental unit comprises two copper atoms (Cu(1), Cu(1A)), four μ₂-bridged CH₃CO₂^- and one ligand molecule. Cu(1) and Cu(1A) are both five-coordinated by four oxygen atoms from four μ₂-CH₃CO₂^- and one nitrogen atom from bridging ligand, forming a distorted square-pyramidal coordination configuration. Cu(1) and Cu(1A) are linked via four μ₂-bridged CH₃CO₂^- anions to form a paddle-wheel structural unit, which furthermore self-assemble into 1D chain via bridging ligands. CCDC: 603429.     

一维梯子状配位聚合物[Na3Er(2，6-PDA)3]·11.5H2O的合成与晶体结构

A novel 1D Ladder-like coordination polymer [Na₃Er(2，6-PDA)₃]·11.5H₂O (2,6-H₂PDA is pyridine-2,6-dicarboxylic acid) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to Monoclinic system with space group P2₁/c, a=0.969 7(3) nm, b=1.914 6(6) nm, c=1.8031(6) nm, β=91.524(5)°, V=3.346 6(18) mm³, Z=4, D_c=1.863g·cm^-3, μ=2.645 mm^-1. The coordination geometry configuration of Er³⁺ center is tricapped trigonal prism. The structures of the title compound exhibit a novel 1D Ladder-like chain.