三个双肼桥连金属配合物的合成,结构和磁性

采用水热合成方法得到3个新的双肼桥连过渡金属化合物：[M（N₂H₄）₂Cl₂]_n（M=Mn（1）,Ni（2））,{[Co_1.5（N₂H₄）₃PO₄（H₂O）]·H₂O}_n（3）,用单晶X射线衍射方法对其晶体结构进行表征。化合物1是以2个肼分子桥联金属Mn和Ni形成1D链状结构,而粉末XRD显示1与2是同构的。化合物3是以2个肼分子桥联金属Co形成1D链,不同的1D链再通过磷酸根PO₄^3-进一步堆积形成3D结构。磁性测试表明肼桥在磁性中心之间传递反铁磁耦合作用。     

三个双肼桥连金属配合物的合成,结构和磁性

采用水热合成方法得到3个新的双肼桥连过渡金属化合物：[M（N₂H₄）₂Cl₂]_n（M=Mn（1）,Ni（2））,{[Co_1.5（N₂H₄）₃PO₄（H₂O）]·H₂O}_n（3）,用单晶X射线衍射方法对其晶体结构进行表征。化合物1是以2个肼分子桥联金属Mn和Ni形成1D链状结构,而粉末XRD显示1与2是同构的。化合物3是以2个肼分子桥联金属Co形成1D链,不同的1D链再通过磷酸根PO₄^3-进一步堆积形成3D结构。磁性测试表明肼桥在磁性中心之间传递反铁磁耦合作用。     

邻苯二甲酸单甲酯双核铜配合物的强反铁磁性和磁构关联研究

以邻苯二甲酸单甲酯(mMP)为配体合成了一个新的双核铜配位化合物[Cu₂(mMP)₂(H₂O)₂]₂·2H₂O (1), 并通过元素分析、红外光谱和X射线单晶衍射等方法对化合物晶体结构进行了表征. 化合物1通过四羧酸桥联的方式形成了桨轮状双金属笼结构. 每个Cu(II)离子采用四方单锥的五配位构型, 其中四个氧原子来自于四个不同的邻苯二甲酸单甲酯配体, 轴向位置上的氧原子则来自于水分子. 配位水分子和溶剂水分子与配体中未配位的氧原子形成了分子间氢键, 并进一步形成三维网络结构. 磁性数据显示双核铜内为强的反铁磁交换作用, 磁耦合作用常数2J=-324 cm^-1. 通过与相关双核铜化合物的对比, 详细分析了化合物的磁构关联并讨论了羧酸类双核铜中强反铁磁性作用的结构因素. 研究表明, 影响羧酸类双核铜强反铁磁性作用的主要结构因素是配体中桥联双核铜的O－C－O部分的电子结构.     

新型含草酰胺桥基的[14]N_4大环的Cu(Ⅱ)-M(Ⅱ)(M=Cu,Ni)双核配合物合成与磁性

合成和表征了四个新的大环上含有草酰胺桥基的双核配合物[Cu(η-L1）ML22］(ClO4)2·nH2O,其中L1为2 ,3 －二羰基－5 ,6 ： 13, 14-二苯基-1 ,4 ,8 , 11－四氮杂十四环－7 , 11－二烯;L2 ＝乙二胺（en）,M=Cu(1),M=Ni（2）;L2 = 1 ,10－邻菲咯啉（phen）,M=Cu(3),M=Ni(4)。测定了配合物（3）和（4）的变温磁化率（4 ．2 －300K）,求得磁参数分别为（3）J＝－99．1 cm－1 和（4）J＝-47．0 cm-1,表明Cu（Ⅱ）、-Cu（Ⅱ）、Cu（Ⅱ）-Ni（Ⅱ）离子间存在反铁磁自旋交换相互作用。     

邻苯二甲酸单乙酯铜配合物的晶体结构与强反铁磁性

A hydrated tetra-carboxylato-bridged dinuclear copper(Ⅱ) complex [Cu₂(mEP)₂(H₂O)₂]₂ (1) (mEp is mono -ethyl phthalate or 1,2-benzenedicarboxylate monoethyl ester) has been prepared and characterized by X-ray diffraction single crystal structure analysis and magnetic measurements. This dinuclear complex adopts dimeric paddle-wheel cage structure and the coordination model around each copper(Ⅱ) atom is square-pyramidal with four oxygen atoms of the carboxylate groups from four different mono-ethyl phthalate ligands and one oxygen atom of water as apical position. The magnetic data for 1 exhibited strong intramolecular antiferromagnetic interaction between the two paramagnetic metal ions with 2J=-315.18 cm^-1. Comparing with other related complexes in structure and magnetic propertity, the main factor which determines the strong antiferromagnetic interaction in the dimeric copper(Ⅱ) carboxylates is the electronic structure of the bridging O-C-O moiety. CCDC: 624561.     

μ-草酰二胺双核铜配合物的合成、结构和磁性

本文合成和表征了2个新的双铜配合物[Cu(oxpn)CuL)(ClO_4)_2,oxpn表示N_(?)N′-双-(3-氨丙基)草酰胺,L为1,10-菲咯啉(phen)或5-硝基-1,10-啉菲咯啉(NO_2-phen)。其中配合物(L=phen)的单晶结构及变温磁化率(4—300 K)已测定,表明该晶体为正交晶系,Pnma空间群,a=10.433(1),b=11.458(2),c=21.999(2),z=4。两个铜离子均处在四角锥配位环境,以草酰二胺桥联,核间相距为5.208。配合物基态为单重态,单-三重态的能差J=—462.92 cm~(-1),表明配合物中两个铜离子间具有强的反铁磁交换作用。     

M,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

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。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，由于硫属于第三周期的元素，其半径较大，电负性较小。     

甲酸根桥联双核铜配合物磁学性质理论研究

基于DFT-BS方法,选择不同的泛函方法和基组,研究anti,anti甲酸桥联双核铜配合物的磁学性质.结果表明,在B3P86/TZV水平计算得到顺磁中心Cu(Ⅱ)离子间磁耦合常数为-55.63 cm^-1,与实验值-55.60 cm^-1最接近,可准确描述甲酸桥联双核铜配合物的磁学性质.顺磁中心Cu(Ⅱ)与甲酸根桥联配体间有较强的轨道作用,其磁轨道主要来源于Cu(Ⅱ)离子的3dyz轨道、桥联配体甲酸根离子的离域π键,顺磁中心Cu(Ⅱ)离子为自旋离域机理.在不同桥联模式的甲酸桥联双核铜配合物中,随顺磁中心Cu(1)自旋密度增加,Cu(Ⅱ)离子间的反铁磁性贡献逐渐增加,其磁耦合常数J值逐渐减小.     

桥联多核配合物的合成及其磁交换作用的评估与预测

本文简述了桥联多核配合物的重要性和研究近况；归纳了该配合物的种类和合成方法；介绍了表征体系中磁交换作用品质和大小的Ｈｅｉｓｅｎｂｅｒｇ方法以及预测该品质和大小的Ｋａｈｎ模型，以典型研究例子说明了这种预测模型在磁性分子设计中的具体应用。     

Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Palladium(I) Complexes

The dinuclear palladium(I) complexes [L(Ar₂HGe)Pd(μ‐GeAr₂)₂Pd(GeHAr₂)L] (Ar=Ph, p‐Tol; L=PMe₃, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge???Ge bond lengths of 2.8263(4) Å (L=PMe₃) and 2.928(1) Å (L=tBuNC), which are close to the longest Ge? Ge bond reported to date [2.714(1) Å]. Significant Ge???Ge interactions between the germylene and germyl ligands (PMe₃ complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe₃ ligands increases the Ge???Ge interaction, and simultaneously activates two Pd? Ge bonds. Adding the chelating diphosphine 1,2‐bis(diethylphosphino)ethane (depe) to the PMe₃ complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.     

含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究

合成了3种双核钌配合物[Ru(bpy)2]2{[(PyCHN)-Ph-O-C6H4-]2R}(ClO4)4,bpy=2,2′-联吡啶,PyCHN=N-2-吡啶亚甲基,R=无(1),-C(CH3)2(2),-SO2(3)并进行了有关表征。电化学研究表明:配合物3的ΔE和Kc值最大,说明苯环和硫原子之间存在着较强的(p(π)-d)π相互作用,有助于获得较强的金属-金属相互作用。配合物1,2,3都有混合价,通过Hush方程可以得到Vab的值大概为320~420 cm-1。这些结果表明:Schiff碱作为桥配体对于调配金属-金属相互作用并将其作为分子导线起着特殊的作用。     

Dinuclear Palladium Complexes with Two Ligand‐Centered Radicals and a Single Bridging Ligand: Subtle Tuning of Magnetic Properties

The facile and tunable preparation of unique dinuclear [(L^?)Pd?X?Pd(L^?)] complexes (X=Cl or N₃), bearing a ligand radical on each Pd, is disclosed, as well as their magnetochemistry in solution and solid state is reported. Chloride abstraction from [PdCl( NNO^ISQ )] ( NNO^ISQ =iminosemiquinonato) with TlPF₆ results in an unusual monochlorido‐bridged dinuclear open‐shell diradical species, [{Pd( NNO ^ISQ)}₂(μ‐Cl)]⁺, with an unusually small Pd‐Cl‐Pd angle (ca. 93°, determined by X‐ray). This suggests an intramolecular d⁸–d⁸ interaction, which is supported by DFT calculations. SQUID measurements indicate moderate antiferromagnetic spin exchange between the two ligand radicals and an overall singlet ground state in the solid state. VT EPR spectroscopy shows a transient signal corresponding to a triplet state between 20 and 60 K. Complex 2 reacts with PPh₃ to generate [Pd(NNO^ISQ)(PPh₃)]⁺ and one equivalent of [PdCl( NNO^ISQ )]. Reacting an 1:1 mixture of [PdCl( NNO^ISQ )] and [Pd(N₃)( NNO^{I SQ})] furnishes the 1,1‐azido‐bridged dinuclear diradical [{Pd( NNO ^ISQ)}₂(κ¹‐N;μ‐N₃]⁺, with a Pd‐N‐Pd angle close to 127° (X‐ray). Magnetic and EPR measurements indicate two independent S=1/2 spin carriers and no magnetic interaction in the solid state. The two diradical species both show no spin exchange in solution, likely because of unhindered rotation around the Pd?X?Pd core. This work demonstrates that a single bridging atom can induce subtle and tunable changes in structural and magnetic properties of novel dinuclear Pd complexes featuring two ligand‐based radicals.     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

Synthesis and Characterization of Bridged Bimetallic Complexes. I. Copper(II) Complexes with Conjugated Diimine Ligands

A series of binucleating Uganda with fully conjugated π-systems have been synthesized. Homobinuclear copper(II) complexes of the form [(Cu(dien)ClO₄)₂L]-(ClO₄)₂, where dien is diethylenetriamine and L is binucleating ligand, were prepared. Mononuclear complexes, with structure similar to that of the preceeding compounds, [Cu(dien)L′(ClO₄)](ClO₄) were synthesized as reference compounds. The infrared spectra, elctronic spectra and magnetic properties were studied. The inductive effect, steric effect and the effect of the length of the conjugated π-system on the magnetic exchange interaction between the two copper ions are discussed. The electrochemical properties of these complexes were investigated by cyclic voltammetry. The copper ions showed the cooperative phenomena and a quasi-reversible sequential transfer of two electrons at the same potential.     

含樟脑衍生物氰基桥联双金属配合物的合成、结构及磁性质

采用樟脑衍生物为配体，分别合成了氰基桥联Cu(Ⅱ)-Fe(Ⅲ)-Cu(Ⅱ)三核配合物[{Cu(D,L-La)₂}₂Fe(CN)₆](ClO₄) (1)和Mn(Ⅲ)-Fe(Ⅲ)双核配合物[Mn(D,L-Lb)(DMF)(Tp)Fe(CN)₃]·(H₂O)₆ (2)。晶体结构分析表明，化合物1中Cu(Ⅱ)离子处于五配位的配位环境，分别和1个D-La，1个L-La及[Fe(CN)₆]^3-中的1个氰基配位，2个Cu(Ⅱ)离子通过[Fe(CN)₆]^3-桥联。通过分子间氢键作用，化合物1形成二维超分子网络结构。化合物2中，[(Tp)Fe(CN)₃]^-通过其中的1个氰基与[Mn(D，L-Lb)]⁺桥联，其中Mn(Ⅲ)离子为六配位，分别和四齿配体Lb的2个氧原子和2个氮原子、DMF的1个氧原子及[(Tp)Fe(CN)₃]^-中的氰基氮原子配位。磁性研究表明，在化合物1中，Cu(Ⅱ)离子与Fe(Ⅲ)离子之间表现出铁磁相互作用，用哈密顿函数H=-2J(S₁·S₂+S₂·S₃)对其χ_MT-T曲线进行拟合，得到1的朗日因子g为2.190，交换常数J为0.55 cm^-1。