新型含氮配体多核铜配合物的合成、晶体结构及其性能研究

以1,10-邻菲罗啉(phen)为配体,采用溶剂蒸发法在水中分别合成了羟基桥连和氯离子桥连的两个新型的含氮配体多核铜离子配合物[Cu4(phen)4(H2O)2(OH)4·(NO3)4·2H2O(1)和Cu2(phen)2Cl4(2)],其结构经元素分析和X-射线单晶衍射表征。1属三斜晶系,空间群P-1,晶胞参数a=10.143 0(9),b=11.900 1(11),c=12.629 9(13),α=111.060(2)°,β=91.070 0(10)°,γ=110.920(2)°,Z=1,V=1 309.8(2)3,F(000)=692。2属单斜晶系,空间群Cc,晶胞参数a=9.860 9(8),b=17.852 9(13),c=13.412 3(15),β=106.583(11)°,Z=4,V=2 263.0(4)3,F(000)=1 256。用荧光光谱和热分析分别研究了1和2的荧光性质和热稳定性,结果表明:在310 nm激发波长激发下,与phen相比,1和2的荧光发射峰分别发生红移和蓝移,λem分别位于451 nm和374 nm。1和2的初始分解温度分别为298℃和300℃。     

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。     

七元杂环桥连联苯化合物的合成、晶体结构及性质的研究Ⅰ．含双氧桥连杂环衍生物的合成与结构表征

合成了一系列含七元内杂环联苯化合物(6，6'位不同取代的2，10-二溴-6H-双 苯[d，f][1，3]双氧杂草和2，10--'醛- 6H-双苯[d，f][1，3]双氧杂草)，通过 元素分析、核磁共振氢谱、紫外可见吸收光谱对它们的结构进行了表征，用X-ray 单晶衍射测定了部分化合物的晶体结构．结果表明这类化合物具有相同的刚性扭曲 构型，其二个苯环扭曲角的大小受6，6，取代基团的影响可以发生8°(35°~43． 1°)的变化。     

Molecular and Polymeric Cadmium Nitrate Complexes with Bridging 3-Aminoquinoline: Synthesis,Structures, and Luminescence Properties

Russian Journal of Coordination Chemistry - The reaction of Cd(NO3)2?4H2O with 3-aminoquinoline (3-Аq) affords the molecular and poly-meric complexes...     

Schiff碱双核Mn配合物的合成、结构和性能研究

Five manganese complexes of Schiff base were synthesized： [Mn^Ⅳ，Ⅳ(μ-O)(Salen)]₂·DMF·H₂O (1)， [Mn^Ⅳ，Ⅳ(μ-O)(5-BrSalen)]₂·DMF·0.5H₂O (2)， {Mn^Ⅳ，Ⅳ(μ-O)[Sal(1，2-pn)]}₂·H₂O (3)， {Mn^Ⅳ，Ⅳ(μ-O)[5-Br-Sal(1，2-pn)]}₂·H₂O (4)， {Mn^Ⅳ，Ⅳ(μ-O)[5-CH₃-Sal(1，2-pn)]}₂·2H₂O (5)， and were characterized by element analysis， IR and UV-Vis spectra. The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and steady high oxide state of manganese. The magnetic properties of 1 and 3 have also been studied. The results show that there is a weak ferromagnetically coupling of Mn^Ⅳ₂ pair at room and low temperature， and the interactions of complex 3 are weaker than complex 1.     

非对称结构的Salen型镍、铜、锰配合物的合成及性质

本文设计合成了两种新型Salen配体H2L1(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2,5-二羟基苯基)-4,5-二甲氧基邻苯二胺)和H2L2(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2-羟基-3,5二叔丁基苯基)-4,5-二甲氧基邻苯二胺)及相应的过渡金属配合物MLn(M=Ni、Cu、Mn;n=1、2)。分别采用核磁、质谱、元素分析、红外光谱和紫外-可见光谱对目标化合物进行了表征。研究了两种配体及其金属配合物的荧光性质,探讨了配体结构及中心金属离子对其荧光性质的影响。研究发现,由于氢键的作用使得配体H2L1的荧光强度远低于H2L2;中心金属离子的嵌入对H2L2的荧光强度有明显的猝灭作用。用循环伏安法研究了配体及其金属配合物的电化学氧化还原性质,并测定了配体及其金属配合物溶液的电导率、摩尔电导率。结果表明,镍、铜、锰配合物的氧化还原过程均为准可逆的单电子过程;且在所研究的配体和配合物中,金属锰配合物溶液的导电能力较强。     

Synthesis,Crystal Structure and Properties of Two Macrocyclic Dinuclear Complexes

Two macrocyclic dinuclear complexes, [Cu₂L¹](PF₆)₂ and [Cu₂L²](ClO₄)₂, were synthesized by cyclo-condensation between N,N′-bis(3-formyl-5-methylsalicylidene)ethylenediimine or N,N′- bis(3-formyl-5-n-butylsalicylidene)ethylenediimine and ethylenediamine in the presence of Cu²⁺ ions. The crystal structures of the complexes were studied. The variable-temperature magnetic susceptibilities and cyclic voltammograms of the complexes were measured. The magnetic and electrochemical properties of the complexes were discussed. The results show that the complexes display very strong antiferromagnetic exchanges and that all copper(II) complexes undergo a one-electron transfer process.     

Synthesis,Structure, and Properties of One-Dimensional Partially Oxidized Tetracyanoplatinate Complexes

The crystal structure of anion-deficient partially oxidized tetracyanoplatinate complexes generally can be classified into one of two categories. The electrical properties of compounds in the two categories are also observed to be different. We have prepared a new complex which does not fall into either of the previous categories. Its synthesis, structure and properties are described.     

Five-, Six-, and Seven-membered Lactim Ethers. Methods of Synthesis and Chemical Properties. (Review)

Data on methods for the production of 5–7-membered lactim ethers and their chemical transformations published after 1970 are reviewed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 645–690, May, 2005.     

七元杂环桥连联苯化合物的合成、晶体结构及性质的研究 I.含双氧桥连杂环衍生物的合成与结构表征

合成了一系列含七元内杂环联苯化合物 ( 6,6′位不同取代的 2 ,10 二溴 6H 双苯 [d ,f] [1,3 ]双氧杂和 2 ,10 二醛 6H 双苯 [d ,f] [1,3 ]双氧杂 ) ,通过元素分析、核磁共振氢谱、紫外可见吸收光谱对它们的结构进行了表征 ,用X ray单晶衍射测定了部分化合物的晶体结构 .结果表明这类化合物具有相同的刚性扭曲构型 ,其二个苯环扭曲角的大小受 6,6′取代基团的影响可以发生 8° ( 3 5°～ 43 .1°)的变化 .     

两种4-溴苯甲酸铽配合物的合成、晶体结构及性质

合成了两种双核铽配合物[Tb(4-BrBA)₂(Phen)(NO₃)]₂ (1)和[Tb(4-BrBA)₃(2,2′-bipy)(H₂O)]₂·2H₂O (2)(4-BrBA=4-溴苯甲酸根,Phen=1,10-邻菲咯啉,2,2′-bipy=2,2′-联吡啶),并用X-射线单晶衍射结构分析方法测定了其晶体结构。这2种配合物均是具有反演中心的二聚体。在四元混配配合物1中,2个Tb³⁺离子被4个4-溴苯甲酸根以双齿桥联和三齿桥联两种方式联结;每个Tb³⁺离子与邻菲咯啉的2个氮原子、硝酸根的2个氧原子和4个桥联4-溴苯甲酸根的5个氧原子配位;Tb³⁺离子的配位数为9。在配合物2中,2个Tb³⁺离子被4个4-溴苯甲酸根以双齿桥联方式联结;每个Tb³⁺离子与2,2′-联吡啶的2个氮原子、水分子的1个氧原子、4个双齿桥联4-溴苯甲酸根的4个氧原子以及1个单齿配位4-溴苯甲酸根的1个氧原子配位;Tb³⁺离子的配位数为8。配合物2中游离水分子与配位水分子以及4-溴苯甲酸根之间形成了氢键,氢键将双核分子2连接成一维链状结构。配合物1和2在紫外灯照射下均发出强烈的绿光,它们的荧光光谱在490、545、585和621 nm处出现4条谱线,这是由Tb³⁺离子的 ⁵D₄ → ⁷F_j(j=6～3)跃迁产生的。     

Synthesis,Crystal Structure and Magnetic Properties of Heptanuclear Manganese Complexes with Schiff-base Ligand

One new mixed-valence heptanuclear manganese complex, [Mn~ⅡMn~Ⅲ6O_2L_6-(NaCH_3COO)_2(CH_3COO)_4](1)(L = 3-ethoxy-6-(((2-hydroxyethyl)imino)methyl) phenol, was synthesized by treating the Schiff-base ligand with Mn(acac)_3?4H_2O and characterized by elemental analysis, IR spectra, thermogravimetric analyses and X-ray single-crystal diffraction. 1 has a similar new mixed-valence heptanuclear structure. The magnetic measurements indicate that 1 exhibits the antiferromagnetic interactions.     

Synthesis,Crystal Structure and Fluorescent Properties of Silver and Cadmium Complexes

Two new complexes [Ag(bix)]n·n NAA·n H_2O(1) and [Cd(NAA)(phen)_2(H_2O)]2· 2CH_3COO-·H_2O(2)(bix = 1,4-bis(imidazol-1-ylmethyl)benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline) have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.     

肉桂酸及其衍生物的Eu(Ⅲ)配合物的合成、结构及荧光性质研究

以肉桂酸C₉H₈O₂(HL)及其衍生物对位取代肉桂酸R-L(R=CH₃,Cl,NO₂,OCH₃,OH)为配体,分别与Eu³⁺配位,得到系列Eu³⁺配合物。X-射线单晶解析结果表明:对甲基肉桂酸铕(1)和对氯肉桂酸铕(2)为一维高分子链,对硝基肉桂酸铕(3)为双核结构。通过FT-IR和UV-Vis光谱分析了配体在配位前后的变化。记录和解析了各配合物的荧光光谱,研究了对位取代基吸电子性和配位小分子对配合物发光性能的影响。     

Synthesis, Structure and Physical Properties of Mn and Cd Complexes with 1,1,2,2-Tetracarboxyl-ethylene Acid

Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd(tce) 0.5(H2O) 3](H2O) (2) fea-tures a pillared layer architecture. The Cd(II) atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd(II) atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901(12) ,b = 8.0212(15) ,c = 8.0769(15) ,α = 108.522(3) ,β = 95.068(3) ,γ = 97.086(3) °,V = 379.92(12) 3,Mr = 456.08,Dc = 1.993 g/cm3,F(000) = 232,μ = 1.748 mm-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I > 2σ(I) . 2 is of monoclinic system,space group P21/c with a = 6.4367(14) ,b = 9.495(2) ,c = 13.907(3) ,β = 117.405(8) °,V = 754.6(3) 3,Mr = 285.51,Dc = 2.513 g/cm3,F(000) = 556,μ = 2.905 mm-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I > 2σ(I).     

肉桂酸及其衍生物的Eu(Ⅲ)配合物的合成、结构及荧光性质研究

以肉桂酸C9H8O2(HL)及其衍生物对位取代肉桂酸R-L(R=CH3,Cl,NO2,OCH3,OH)为配体,分别与Eu3+配位,得到系列Eu3+配合物。X-射线单晶解析结果表明:对甲基肉桂酸铕(1)和对氯肉桂酸铕(2)为一维高分子链,对硝基肉桂酸铕(3)为双核结构。通过FT-IR和UV-Vis光谱分析了配体在配位前后的变化。记录和解析了各配合物的荧光光谱,研究了对位取代基吸电子性和配位小分子对配合物发光性能的影响。     

含S,N杂环戊烯桥头的二芳烯光致变色化合物的合成及性质研究

光致变色材料是目前光功能材料领域中研究的热点之一.在众多的光致变色体系中,二芳烯化合物因其良好的热稳定性和抗疲劳性使其在信息光存储及分子光开关等领域有着广泛的应用前景.     

具有不同类型桥基的双核Cu(Ⅱ)-Schiff碱配合物的合成和晶体结构

合成了３个分别以Ｃ２Ｏ２－４（［Ｃｕ２（Ｌ１）２（ｏｘ）］，１），ＡｃＯ－（［Ｃｕ２（ＡｃＯ）（Ｌ２）２］ＢＦ４，２）和酚氧（［Ｃｕ２（Ｌ３）２］（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物［Ｃｕ２（Ｌ１）２（ｏｘ）］·［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ（１′）及２和３的晶体结构．Ｘ射线衍射结果表明：１′，２和３分别属于Ｆｄｄｄ，Ｐ２１／ｃ和Ｐ２１／ｃ空间群．晶胞参数：［Ｃｕ２（Ｌ１）２（ｏｘ）］［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ，ａ＝２．４３９０（４）ｎｍ，ｂ＝３．０５３８（６）ｎｍ，ｃ＝１．８４９４（６）ｎｍ，α＝β＝γ＝９０．００°；２，ａ＝０．８４７（１）ｎｍ，ｂ＝２．６５４２（８）ｎｍ，ｃ＝１．４１００（６）ｎｍ，β＝９１．３４（６）°；３，ａ＝０．７６４６（３）ｎｍ，ｂ＝１．６９８３（３）ｎｍ，ｃ＝２．４４１７（３）ｎｍ，β＝９７．１１°     

Synthesis,Structure and Photophysical Properties of Heteronuclear Pt_2Cu Alkynyl Complexes

Two luminescent hetero-trinuclear complexes [Pt2Cu(μ-dpppy)2(C≡CC6H4R-4)4](Cl O4)(R = H,1;R = CH3,2;dpppy = 2,6-bis(diphenylphosphino)pyridine) have been synthesized and characterized by elemental analyses,ESI-MS,1H and 31P{1H} NMR spectroscopy,and X-ray crystallography for 2.Their photophysical properties in the solid state and in solutions at room temperature and in frozen glasses at 77 K were studied.Both complexes 1 and 2 show strong orange-red emission in the solid state at room temperature and in frozen glasses at 77 K,and weak emission in solutions.