系列双核Ln(III)配合物的晶体结构和磁性

合成了分子式为[Ln~2(phen)~2L],phen=C~1~2H~8N~2[ALn=Nd,L=(CH~3COO)~4(ONO~2)~2,BLn=Sm,L=(C~6H~5COO)~6,CLn=Eu,L=(C~6H~5COO)~6]3种同双核配合物。用X射线四圆衍射仪测定了3种化合物的结构。在化合物A分子中,2个Nd(III)原子由4个CH~3COO^-基团桥联,以phen和ONO~2^-为端基,构成了一个具有C~2对称性的双核分子。配合物B和C具有完全相同的结构,它们是以4个苯甲酸根为桥,2个phen和2个C~6H~5COO^-为端基的中心对称双核分子,其中6个苯甲酸根的成键状态可分为3种状况。在3种化合物中,每个Ln均为9配位,呈不规则多面体。Ln-Ln距离,A为0.397nm,B和C均为0.405nm。测定了各配合物的变温磁化率,通过对磁性质研究,发现化合物A在低温下具有反铁磁物质行为,并由理论拟合,求得了磁参数g,J值。     

系列双核Ln(Ⅲ)配合物的晶体结构和磁性

合成了分子式为[Ln2(phen)2L],phen=C12H8N2[A Ln=Nd,L=(CH3COO)4(ONO2)2,B Ln=Sm,L=(C6H5COO)6,C Ln=Eu,L=(C6H5COO)6]3种同双核配合物.用X射线四圆衍射仪测定了3种化合物的结构.在化合物A分子中,2个Nd(Ⅲ)原子由4个CH3COO-基团桥联,以phen和ONO2-为端基,构成了一个具有C2对称性的双核分子.配合物B和C具有完全相同的结构,它们是以4个苯甲酸根为桥,2个phen和2个C6H5COO-为端基的中心对称双核分子,其中6个苯甲酸根的成键状态可分为3种状况.在3种化合物中,每个Ln均为9配位,呈不规则多面体.Ln-Ln距离,A为0.397nm,B和C均为0.405nm.测定了各配合物的变温磁化率,通过对磁性质研究,发现化合物A在低温下具有反铁磁物质行为.并由理论拟合,求得了磁参数g,J值.     

铂-双(二苯基膦)甲烷双核配合物的晶体结构

本文报道了一种trans-双铂双膦配合物的单晶结构.配合物中dppm以桥联方式与金属配位,形成一个八元环的骨架结构 .     

稀土双核配合物的合成与磁性

稀土离子存在于许多磁性材料中,但至今稀土双核配合物的合成及磁性研究很少,建立磁性-结构间的关系对新型分子磁性材料的设计有重要意义。稀土双核配合物的磁性研究也为研究f轨道参与磁相互作用提供第一手材料。我们曾合成了一系列以氯冉酸二价阴离子为桥联配体的过渡金属双核配合物,本文合     

配合物[Ln(CH3COO)2(NO3)(bipy)]2的合成与晶体结构

合成了５种新型镧系四元混合阴离子配合物,用Ｘ射线四圆衍射仪测定了［Ｐｒ（ＣＨ３ＣＯＯ）２（ＮＯ３）（ｂｉｐｙ）］２的晶体结构,四个醋酸根呈两种配位方式,测定了铕和钆配合物的荧光和ＥＳＲ谱．     

三足七齿Schiff碱铈(Ⅲ)双核配合物的晶体结构和性质研究

制备了Schiff碱型三足体配体H₃Brapi,通过溶剂热方法合成了Ce(Ⅲ)的双核配合物[Ce(Brapi)]₂·2DMF,利用元素分析、红外光谱、紫外光谱和荧光光谱等进行了表征,并用X-射线单晶衍射测定了其晶体结构,结果表明,配合物晶体属单斜晶系,P2₁/n空间群,a=1.166 7(3) nm,b=1.348 29(3) nm,c=2.086 9(5) nm,β=96.314°,Z=2,V=3.263 0(14) nm³,D_c=1.849 Mg·m^-3,R₁=0.035 9,wR₂=0.103 6。2个配体桥联2个金属形成一种具有反演对称性的夹心式双核结构,其中每个Ce(Ⅲ)的配位环境N₄O₄都是一种四方反棱柱多面体,Ce-Ce距离为0.397 1 nm。在2～300 K范围内测定了配合物的变温磁化率,结果表明,在配合物中Ce(Ⅲ)离子间存在反铁磁性相互作用。荧光光谱分析表明,配合物的荧光属于L*-L跃迁的发光类型。     

铕(Ⅲ)-锌(Ⅱ)双核配合物的合成和表征

Two new Eu(Ⅲ)-Zn(Ⅱ) binuclear complexes Zn(Salen)EuL₃ have been synthesized, where Salen=Shiff base of bissalicylaldehyde with ethlenediamine and L=acetylacetone (for complex Ⅰ) or trifluoroacetylacetone (for compelx Ⅱ). Analytical experimetal such as IR, UV and elemental analysis suggest the possible component and structure, the fluorescence spectrum of the complex Ⅱ suggests the M^*→M fluorescence mechanism.     

系列双核稀土配合物的合成、晶体结构及光物理性质

本文采用水热法合成了4种双核稀土配合物[Y₂(p-MBA)₆(Phen)₂] (1)、[Y₂(p-ClBA)₆(Phen)₂] (2)、[Pr₂(BA)₆(Phen)₂](3)和[Pr₂(p-ClBA)₆(H₂O)₂(Phen)₂](4)[Phen=邻菲咯啉、p-MBA=对甲基苯甲酸、BA=苯甲酸、p-ClBA=对氯苯甲酸]。测定了4种配合物的单晶结构。4种配合物在结构和配位方式上有很多的相似之处,它们的晶体都属于三斜晶系,P1空间群。在分子中,每个稀土离子与1个邻菲咯啉分子螯合,2个稀土离子均以苯甲酸根或其衍生物为桥。但是,桥连配体的数目以及配体的配位方式不尽相同。配合物4中配位水分子与对氯苯甲酸根之间形成了氢键,氢键将双核配合物4连接成二维层状网络结构。对4种配合物的UV-Vis-NIR、IR和荧光性质进行了测定和对比分析。配合物1和2的荧光指认为LLCT和LMCT,而配合物3和4的荧光表现出LLCT与LMCT混合跃迁及Pr³⁺的特征发射。     

含螯合配体的钕配合物的晶体结构

用NdCl_3,NaS_2CNEt_2和Et_4NBr为原料,在甲醇溶剂中反应,生成钕配合物,[Et_4N](Nd(S_2CNEt_2)_4]晶体,用X-射线衍射法测定了配合物的晶体结构。晶体属于单斜晶系,空间群P2_1/n晶胞参数,a=11.704(3)A,b=20.941(3)A,c=17.564(4)A,V=4242.2A~3,Z=4。结构经最小二乘方法修正后偏离因子为R=0.0564.在配合物钕离子是通过8个硫原子配位形成扭曲的NdS_3核的十二面体。井对配合物的红外线光谱和紫外可见光谱也进行了研究。     

Synthesis, characterization and magnetism of binuclear cobalt (II) complexes bridged by tetracarboxylato groups

Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti     

Structures of bis(cyclopentadienyl) binuclear titanium complexes

The (C₅H₄-XMe₂-C₅H₄) · (TiCl₃)₂ binuclear complexes, where X = Si (1) or C (2), have been studied by X-ray structural analysis. In both structures, the coordination polyhedra about the Ti atoms are distorted tetrahedra formed by three CI atoms and one Cp ring. The conformations of molecules1 and2 and the possibility of the occurrence of secondary Ti-Cp...Cl-Ti interaction are discussedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2269–2271, September. 1996.     

Synthesis, characterization and magnetism of μ-chloranilato bi-nuclear chromium (III) complexes

Five new chloranilato-bridged binuclear chromium (III) complexes have been synthesized and identified as [Cr2(CA)L4]-(ClO4)4[L denotes 5-methyl-1,10-phenanthroline (Me-phen); 2,9-dimethyl-1, 10-phenanthroline ( Me2-phen); 5-chloro-1,10-phenanthroline(Cl-phen); diaminoethane (en) or 1,3-diaminopropane (pn)], where CA represents the dianion of chloranilic acid. Based on elemental analyses, molar conductivity and magnetic moment of room-temperature measurements, and IR and electronic spectral studies, it is proposed that these complexes have CA-bridged structures and consist of two chromium (III) ions, each in an octahedral environment. The complexes [Cr2(CA)(Me-phen)4](ClO4)4(1) and [Cr2(CA)(Me2-phen)4](ClO4)4(2) were further characterized by variable temperature (4.2-300 K) magnetic susceptibility measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, , giving the exchange parameter J = -7.8 cm-1 for (1) and J= -6.5 cm*1 for (2). This result     

Crystal Structures of Ln（NO3）3（Ln=La,Yb）Complexes with 12—crown—4

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｓｏｆＬｎ（ＮＯ_３）_３（Ｌｎ＝Ｌａ，Ｙｂ）Ｃｏｍｐｌｅｘｅｓｗｉｔｈ１２－ｃｒｏｗｎ－４ＭａｏＪｉａｎｇ－Ｇａｏ；ＪｉｎＺｈｏｎｇ－Ｓｈｅｎｇ；ＹｕＦｅｎｇ－Ｌａｎ（ＬａｂｏｒａｔｏｒｙｏｆＲａｒｅＥａｒｔｈＣｈｅｍ...     

Synthesis and magnetic properties of copper (II)-lanthanoid (III) binuclear complexes with N,N′-bis(3-aminopropyl) oxamido ligand

Six novel μ-oxamido binuclear complexes, namely Cu(axpn)Ln(L)₂(ClO₄)₃ (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro,10-phenanthroline (abbreviated as NO₂-phen), have been synthesized and characterised. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO₂-phen)2(ClO₄)₃.2H₂O was measured over the 4–300 K and the observed data were successfully simulated by equation based on spin Hamiltonian operator (H = -2J₁ · S₂), giving the exchange integral J(Cu-Gd)=-1.62 cm^?1. This indicates a weak antiferromagnetic interaction between the Cu(II) and Gd(III) ions.     

Synthesis and Crystal Structure of Binuclear Complex of Copper(Ⅱ)Chloroacetate with Acetamine

１ＩＮＴＲＯＤＵＣＴＩＯＮＣｏｐｐｅｒｃｏｍｐｌｅｘｅｓｈａｖｅａｌａｒｇｅｖａｒｉｅｔｙｏｆｓｔｅｒｉｃｓｔｒｕｃｔｕｒｅｓａｎｄｐｌａｙａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｃａｔａｌｙｓｉｎｇｔｈｅｅｎｚｙｍａｔｉｃａｃｔｉｖｉｔｉｅｓ，ｗｈｉｃｈ...     

Ferromagnetic interactions in EO-azido-bridged binuclear transition metal(II) systems: Syntheses, crystal structures and magnetostructural correlations

Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-1H-pyrazol-1-yl)ethane (bppe), formulated as [M 2 (N 3 ) 2 (bppe) 2 ](ClO 4 ) 2 (M = Co, 1; Ni, 2; Cu, 3), were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode (EO), with the M-N EO -M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the temperature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic interactions [J = 26.32 cm-1 (1), J = 38.23 cm-1 (2) and J = 139.83 cm-1 (3)]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.     

Trigonal (-3) symmetry octahedral lanthanide(III) complexes of zwitterionic tripodal ligands: luminescence and magnetism

Sandwich coordination complexes, [Ln^III(H₃L)₂]X₃?solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5-n-butyl benzoate)aminoethyl)-amine (H₃L¹) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H₃L²). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [Ln^III(H₃L)₂]X₃?solvents (L = L¹, L²; X = Cl^?, NO₃^?; solvents = MeOH or H₂O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [Tb^III(H₃L¹)₂]Cl₃·6MeOH, [Dy(H₃L¹)₂]Cl₃·6MeOH, [Eu^III(H₃L¹)₂]Cl₃·6MeOH and [Tb^III(H₃L¹)₂](NO₃)₃ reveal high-crystallographic ?3 symmetry at the O₆-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [Tb^III(H₃L¹)₂]Cl₃·MeOH·3H₂O, [Dy^III(H₃L¹)₂]Cl₃·6H₂O, [Ho^III(H₃L¹)₂](NO₃)₃·2H₂O, [Er^III(H₃L¹)₂]·H₂O and [Tb^III(H₃L¹)₂](NO₃)₃ down to 2.0 K.     

Synthesis and magnetic studies of phthalato-bridged oxovanadium(IV) binuclear complexes

Six new μ-phthalato binuclear oxovanadium(IV) complexes, namely [(VO)₂(PHTH)-(L)₂]SO₄ (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me₂ bpy); 5-nitro-1,10-phenanthroline (NO₂-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-1,10-phenanthroline (CH₃-phen), where PHTH is the phthalate dianion), have been synthesized and characterized by elemental analyses, IR, electronic spectra, magnetic moments at room temperature and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complexes [(VO)₂(PHTH)(phen)₂]SO₄ (1) and [(VO)₂(PHTH)(CH₃-phen)₂]SO₄ (2) was measured in 4—300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, ?=?2J?₁·?₂, giving the exchange integrals J=?12.8 cm^?1 for 1 and J=?7.9 cm^?l for 2. This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.