2-乙酰基吡啶缩异烟酰腙镍(Ⅱ)和铜(Ⅱ)配合物的合成、晶体结构与性质

采用常规溶液法合成了2-乙酰基吡啶缩异烟酰腙镍配合物[NiL₂](1)和铜配合物[Cu(Ac)L](2),采用元素分析、红外光谱、紫外光谱、荧光光谱和热重分析以及X-射线单晶衍射分析进行了表征.结果表明,1的晶体属正交晶系,Aba₂空间群,晶胞参数a=1.2059(3)nm,b=2.0741(5)nm,c=0.9115(2)nm,V=2.2798(10)nm³,Z=4;中心离子Ni(Ⅱ)的配位数为6,它处于畸变八面体配位环境.2属单斜晶系,P2₁/c空间群,晶胞参数a=0.86477(13)nm,b=1.3383(2)nm,c=1.3631(2)nm,β=105.650(4)°,V=1.5190(4)nm³,Z=4;中心离子Cu(Ⅱ)的配位数为5,它处于畸变四方锥配位环境,吡啶基与金属配位的结果使配合物形成一种Z形配位聚合物.配合物有很高的热稳定性,分解温度分别为340℃(1)和296℃(2).2-乙酰基吡啶缩异烟酰腙没有发光性质,而配合物1和2均可发射紫色荧光     

一个不常见的Ni(Ⅱ)的戊三酮二水杨酰腙配合物的合成和晶体结构

合成了镍的戊三酮二水杨酰腙配合物Ni(C₁₉H₁₆N₄O₅)的两个同质异晶,测定其晶体结构。该配合物的两个晶体均属单斜晶系,空间群为C2/c,晶体1晶胞参数为:a=1.03076(9)nm,b=1.9105(1)nm,c=0.93305(8)nm,β=101.490(4)°,Z=4,μ=1.119mm^-1,R=0.0370;晶体2晶胞参数为:a=2.1949(3)nm,b=0.9901(2)nm,c=0.8568(1)nm,β=92.799(6)°,Z=4,μ=1.084mm^-1,R=0.0440。两个晶体中镍原子由多啮配体的二个酰氧原子和二个肼氮原子形成平面正方形配位。对配合物的红外光谱进行归属。     

由喹喔啉类配体构筑的钴的配合物的水热合成及晶体结构

采用水热法合成了一个配合物[Co(AIP)(HAIP)₂]·(OH)₂(HAIP=2-(9-anthryl)-1H-imidazo[4,5-f][1,10] phenanthroline)1, 并对其进行了元素分析、红外光谱、热重表征和X射线单晶衍射测定。配合物1属于单斜晶系, 空间群为C2/c, 晶胞参数为:a=1.152 9(2), b=3.673 6(7), c=1.584 1(3) nm, α=107.73(3)°, V=6.382(2) nm³, Z=4(291(2) K)。在晶体中, 中心离子Co(Ⅲ)分别与来自于2个不同的HAIP配体和1个AIP 配体上的6个氮原子形成六配位的变形八面体构型。     

三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz^*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu₂(mpz^*eaT-EtO)₂(N₃)₂Cl₂(1)和Cu₂(mpz^*eaT-MeO)₂(N₃)₄(2)(mpz^*eaT-EtO：2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz^*eaT-MeO：2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.9949(2)nm,b=1.0216(2)nm,c=1.1480(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.9460(3)nm³,Z=1;配合物2属于单斜晶系,P2₁/c空间群,a=1.5464(5)nm,b=1.4008(5)nm,c=0.8905(3)nm,β=103.227(5)°,V=1.8779(10)nm³,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

五配位单核钴配合物的单晶结构和磁性能

制备了五配位单核钴配合物[Co（TMC）Cl]ClO₄（1,TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane）。配合物1结晶于单斜晶系：P2₁,晶胞参数为a=0.805 95（7）nm,b=1.486 58（12）nm,c=0.813 64（7）nm,β=110.190（2）°,V=0.914 93（13）nm³,Z=2,T=120（2）K。钴与来自TMC配体的4个氮原子和1个氯离子配位,形成了扭曲的四方锥配位构型。磁性测试揭示了高自旋的钴离子具有场诱导的慢弛豫行为。     

二氯·双(N, N-二乙基-2-辛硫基乙酰胺)合钯(Ⅱ)配合物的合成及其结构

在有机溶剂中合成了反式-[Pb(DEOTA)₂Cl₂],C₂₈H₅₈N₂O₂Cl₂S₂Pd,对配合物进行了组成分析、摩尔电导、差热-热重、紫外、红外等测试,并经X射线单晶结构分析,确定了配合物的结构.配合物晶体属单斜晶系,空间群C₂/ca=32.513(9)Å,b=12.174(3)Å,c=9.798(4)Å,β=106.27(3)°,V=3722(1)ų,Z=4,D_c=1.24g·cm^-3.     

一种水杨醛异烟酰腙及其锌配位聚合物的合成、晶体结构和荧光性质

合成了一种酰腙类Schiff碱4-(二乙胺基)水杨醛异烟酰腙(H₂L·H₂O,1)并制备了它的锌配合物[Zn(L)(Phen)]_∞(2),用元素分析、红外光谱、紫外光谱、荧光光谱和X-射线单晶衍射分析等手段进行了表征.1的晶体属三斜晶系,P1空间群,晶胞参数a=0.71058(4)nm,b=1.0045(2)nm,c=1.3054(3)nm,α=97.383(11)°,β=102.989(12)°,γ=104.038(10)°,V=8.641(3)nm³,Z=2;分子间通过氢键作用形成一维链超分子体系.2的晶体属三方晶系,P3₁空间群,晶胞参数a=1.68654(12)nm,b=1.68654(12)nm,c=0.79656(12)nm,V=1.9622(5)nm³,Z=3;配合物结构基元由1个锌离子、1个邻菲咯啉和1个酰腙组成,通过吡啶环的桥联作用形成一种双螺旋状配位聚合物.1和2都能发射绿色荧光,最大发射波长分别为524和535nm.     

2-(4-甲基苯甲酰基)苯甲酸构筑的锰(Ⅱ)配合物的晶体结构、电化学、荧光及磁性研究

以2-(4-甲基苯甲酰基)苯甲酸(HL)为配体合成了一个新的锰((Ⅱ)配合物Mn(L)₂(2,2'-bipy)₂。该配合物晶体属单斜晶系,空间群P2₁/c,晶胞参数：a=1.7198(2)nm,b=1.03980(14)nm,c=2.3463(3)nm,β=95.732(3)°,V=4.1748(9)nm₃,D_c=1.346g·cm^-3,Z=4,μ(MoKα)=0.373mm^-1,F(000)=1756,最终偏离因子R₁=0.0423,wR₂=0.0949。标题配合物的中心锰(Ⅱ)离子处于变形的八面体配位环境中。测定了配合物的电化学、荧光和磁性。结果表明：在循环伏安过程中,配合物的电子转移是准可逆的,对应的电极反应是Mn(Ⅲ)/Mn(Ⅱ);配合物在536~556nm之间有一个较强的荧光发射峰;在300~2K,配合物有反铁磁性。     

异核配合物[Co(Ⅲ)(Hdmg)2(H2O)2Mn(Ⅱ)Cl3]的合成与晶体结构

A new coordination compound Co(Ⅲ)(Hdmg)₂(H₂O)₂Mn(Ⅱ)Cl₃ was synthesized and its crystal structure was determined. The crystal data are as follows: crystal system, orthorhombic; space group, C222₁(#20); a=1.18315(3) nm, b=1.28631(5) nm, c=1.14355(2) nm, V=1.74037(9) nm³, Z=4, D_c=1.857 g·cm^-3, F(000)=980.00, μ(MoKα)=21.69 cm^-1, R₁=0.030, wR₂=0.92. The coordination geometries around Co(Ⅲ) and Mn(Ⅱ) atoms are distorted octahedral and distorted trigonal bipyramidal, respectively. The Hdmg chelates Co(Ⅲ) and bridges to two Mn(Ⅱ) atoms to form a polyheteronuclear helical structure along the c axis.     

2-甲酰基呋喃苯乙酰腙及其Ni(Ⅱ)配合物的晶体结构及热化学性质

以苯乙酸甲酯、水合肼和呋喃甲醛为原料, 合成了配体2-甲酰基呋喃苯乙酰腙(H₂L：C₁₃H₁₂N₂O₂), 再与六水氯化镍反应, 制得配合物Ni(HL)₂ (1), 并对配体及配合物进行了元素分析和X射线单晶衍射结构表征, 结果表明, 配体晶体属单斜晶系, P2₁/c空间群, 晶胞参数为：a=1.161 9(3) nm, b=1.359 8(3) nm, c=0.792 16(19) nm, β=109.307(4)°;Ni(Ⅱ)配合物晶体属三斜晶系, P1 空间群, 晶胞参数为：a=0.455 70(14) nm, b=1.094 7(3) nm, c=1.204 8(4) nm, β=98.302(5)°。利用热重实验研究了H₂L和1的热稳定性, 并计算了各自热分解过程的表观活化能(Ea), 发现配合物的热稳定性要远高于配体。采用微量热法研究了H₂L及1与小牛胸腺DNA(CT-DNA)的相互作用, 实验结果表明, 配合物的作用焓值(ΔH)要大于配体的焓值, 说明配合物与CT-DNA的作用要比配体与CT-DNA的作用更强。     

Two new dinuclear complexes with dipicolinate and bridging 2-aminopyrazine ligands: preparation,structural, spectroscopic,and thermal characterizations

Treatment of an aqueous solution of dipicolinic acid (dipicH₂) and 2-aminopyrazine (apyz) with Cu(NO₃)₂?·?3H₂O or ZnCl₂ (in molar ratio 1?:?1?:?1) led to formation of dinuclear complexes, [M₂(H₂O)₄(dipic)₂(µ-apyz)] (M?=?Cu (1) and Zn (2)). Both complexes were characterized by elemental analyses, IR, and UV-Vis spectroscopy. Their molecular and crystal structures were determined by X-ray crystal structure analysis and their thermal stabilities were confirmed by TGA/DTA methods. Complex 1 crystallizes in the triclinic P-1 space group, while 2 crystallizes in the monoclinic P2₁/c space group. The dinuclear complexes are analogous and composed of two metal ions bridged by 2-aminopyrazine. Each M(II) is coordinated by one nitrogen atom and two oxygen atoms of tridentate dipicolinate, one heterocyclic nitrogen of 2-aminopyrazine, and two coordinated water molecules. The resulting geometry for the MN₂O₄ coordination environment can be described as distorted octahedral. Extensive hydrogen-bonding interactions involving all water ligands, dipicolinate oxygen atoms, and amino groups further stabilize the complex units by linking them to form 3-D networks for 1 and 2.     

In situ synthesis,crystal structures,and luminescence of two new tetrazole complexes

The synthesis, crystal structures, and luminescent properties of two new complexes containing tetrazolyl ligands are described. Refluxing a mixture of fipronil (fipronil = (±)-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), sodium azide, and CuCl₂ in ethanol and water gives complex 1, [M(L)₂](H₂O)₂] ? 2H₂O (HL = (±)-5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-tetrazole, M = Cu). Hydrothermal reaction of fipronil, sodium azide, and Cd(ClO₄)₂ in the presence of water and ethanol (Demko–Sharpless tetrazole synthesis) yields 2, [M(L)₂](H₂O)₂] ? 2H₂O (M = Cd). The metals in both complexes are six coordinate from two water molecules, two nitrogens from different tetrazolyl groups, and two nitrogens from pyrazolyl groups. Photoluminescence studies reveal that 2 exhibits strong blue fluorescent emission at λ _max = 451 nm in solid state at room temperature.     

含N-苯甲酰皮考林酰肼的钒酰、镍及锰配合物的合成和晶体结构

合成了3个含N-苯甲酰皮考林酰肼(简写为HL)的钒、镍和锰配合物[VO_2L](1,C_(13)H_(10)N_3O_4V,M_r=323.18),[NiL_2]·0.5CH_3OH(2,C_(26.5)H_(22)N_6NiO_(4.5),Mr=555.21)和[MnL_2]·0.5CH_3OH(3,C_(26.5)H_(22)MnN_6O_(4.5),Mr=551.44)。配合物1属三斜晶系,空间群为P1,a=0.71241(3)nm,b=0.89625(6)nm,c=1.11706(6)nm,α=94.715(2)°,β=102.053(2)°,γ=112.375(3)°,V=0.63461(7)nm~3,Z=2,F(000)=328,μ(MoKα)=0.802mm~(-1),R=0.0290,wR=0.0816;配合物2属单斜晶系,空间群为C2/c,a=2.5875(1)nm,b=1.4868(1)nm,c=1.8353(1)nm,β=134.470(4)°,V=5.2081(5)nm~3,Z=8,F(000)=2368,μ(MoKα)=0.795mm~(-1),R=0.0459,wR=0.1330;配合物3属单斜晶系,空间群为C2/c,a=2.60113(3)nm,b=1.45231(4)nm,c=1.92903(1)nm,β=132.824(1)°,V=5.3448(2)nm~3,Z=8,F(000)=2344,μ(MoKα)=0.543mm~(-1),R=0.0457,wR=0.1325。在配合物1中,钒(V)原子具有畸变的N_2O_3四角锥配位构型,晶体内每两个分子通过分子间氢键作用形成缔合分子对。在配合物2和配合物3中,镍(Ⅱ)原子和锰(Ⅱ)原子具有扭曲的N_4O_2八面体配位构型,晶体通过分子间氢键作用形成一维的无限链状结构。红外光谱表明,配体在形成配合物后,ν(C=O)和ν(C=N)红移。电     

Organodiiron(II)-complexes containing a long conjugated hydrazonato spacer. Synthesis, characterization, electrochemical and structural studies

Organometallic hydrazines of general formula [(η⁵-Cp)Fe(η⁶-p-RC₆H₄NHNH₂)]⁺PF₆⁻ (Cp=C₅H₅; R=H, (1)⁺PF₆⁻; Me, (2)⁺PF₆⁻; MeO, (3)⁺PF₆⁻; Cl, (4)⁺PF₆⁻) react with equimolar quantities of (E)-4-(2-ferrocenylvinyl)-benzaldehyde, (E)-[(η⁵-Cp)Fe(η⁵-C₅H₄)CHCHC₆H₄CHO], to afford stereoselectively, the new homodimetallic hydrazones formulated as (E)-[(η⁵-Cp)Fe(η⁶-p-RC₆H₄)NHNCHC₆H₄CHCH(η⁵-C₅H₄)Fe(η⁵-Cp)]⁺PF₆⁻ (R=H, (5)⁺PF₆⁻; Me, (6)⁺PF₆⁻; MeO, (7)⁺PF₆⁻; Cl, (8)⁺PF₆⁻). These compounds were fully characterized by elemental analysis and spectroscopic techniques (¹H- and ¹³C-NMR, IR and UV-vis) and, in the case of complex (6)⁺PF₆⁻, by single crystal X-ray diffraction methods. The rotations of the ferrocenyl unit by 37.2° out of the NHNCHC₆H₄CHCH spacer and coordinated phenyl ring planes, may generate an unfavorable structure to allow π-electron delocalization along the entire hydrazonato backbone between the two metals separated through bonds by more than 1.8 nm, as confirmed by the electrochemical data.     

混杂[2, 3, 9, 10, 16, 17, 23, 24-八(庚基)酞菁][四(4-吡啶 基)卟啉]合钇 (III)二层配合物的合成及其谱学和电化学性质

用四(4-吡啶基)卟啉(H~2TPyP)与乙酰丙酮钇(III)[Y(acac)~3.H~2O]反应,生成单层配合物Y(TPyP)(acac)。将其与4,5-二(庚基)二氰基苯混和,后者在DBU催化下发生四聚反应,生成混杂[2,3,9,10,16,17,23,24-八(庚基)酞菁][四(4-吡啶基)卟啉]合钇(III)二层配合物Y(TPyP)[Pc(C~7H~1~5)~8]。该化合物用紫外-可见、近红外、红外及质谱等进行了表征,并用循环伏安法(CV)和差示脉冲法(DP)研究了其电化学性质。     

Thermo-XRD-analysis and peptization study of the adsorption of alizarinate by Co-, Ni-, and Cu-montmorillonite

The adsorption of the monovalent anionic dye alizarinate onto Co-, Ni- and Cu-montmorillonite was carried out by adding the dye into aqueous clay suspensions. During the loading of the clay suspension by alizarinate, only some of the added organic anion is adsorbed by the clay forming d-coordination chelate complexes on the clay surface. Maximum adsorption of Co-, Ni- and Cu-clay were 13, 13 and 25 mmol dye per 100 g clay. Since the capacity of the clay for these transition metal cations is 38 mmol per 100 g clay, these saturations indicate that only part of the transition metal cations form positively charged d-coordination chelate complexes with metal:ligand ratio of 1. The complex cations can be located inside the interlayer spaces or on the broken bonds surfaces. Thermo-XRD-analysis and peptization studies of the solids and the clay water systems respectively were used here to identify the sorption sites. The Co and Ni complexes were obtained on the broken bonds surfaces whereas the Cu complexes were obtained in the interlayer space. Co²⁺, Ni²⁺ and Cu²⁺ were extracted from the clay into suspensions containing excess alizarinate.     

Synthesis and Crystal Structure of Potassium triaqua（ethyleneamin—N,N,N‘,N’—tetraacetate）gadolinium（Ⅲ）pentahydrate

1 INTRODUCTION The chemistry of lanthanide (Ⅲ) complexes has a considerable history. The stereochemistry of the lanthanide (Ⅲ) complexes with ethyleneamine- N, N, N, N-tetraacetate (Edta) has been investigated[1~10]. Up to now, many Ln-Edta complexes with the chemical formulae of M[Ln(Edta)(H2O)m]nH2O (M = Na+, K+, Cs+, NH4+, Guanium; m = 2, 3; n = 0, 1, 3, 5) have been reported and suggested that the coordination modes and crystal systems for the Ln-Edta complexes depend on …     

Synthesis and Characterization of Transition Metal (Cu,Co, Fe) Complexes of 6-Methyl-5-arylhydrazono-2-thio-4-oxo-pyrimidine Ligand

The article deals with a study to synthesize transition metal complexes of copper, cobalt, and iron with the ligand 6-methyl-5-arylhydrazono-2-thio-4-oxo-pyrimidine (MATOPyr). The synthesized ligand and all metal complexes were characterized by elemental analysis, XRD, SEM, FTIR, ¹HNMR, UV-VIS, magnetic spectral studies, and Mössbauer measurements. The morphology of the ligand along with the complexes of all three metals was also deduced.     

系列同三核铬、锰、铁羧酸配合物的FAB-MS研究

进行了系列同三核羧酸配合物〔Ｍ３Ｏ（Ｏ２ＣＲ）６Ｐｙ３〕Ｘ（Ｍ＝Ｃｒ,Ｍｎ,Ｆｅ;Ｒ＝ＣＨ３,Ｃ２Ｈ５,Ｃ６Ｈ５;Ｘ＝Ｃｌ－,ＣｌＯ４－;Ｐｙ为吡啶）的快原子轰击质谱（ＦＡＢ－ＭＳ）研究。获得了包括配位吡啶在内的完整阳离子峰。在研究其断裂规律时,主要观察到４个系列碎片离子：Ⅰ．〔Ｍ３Ｏ（Ｏ２ＣＲ）ｎ〕＋,ｎ＝６～２;Ⅱ．〔Ｍ３Ｏ（Ｏ２ＣＲ）ｎＯ〕＋,ｎ＝５～１;Ⅲ．〔Ｍ２Ｏ（Ｏ２ＣＲ）ｎ〕＋,ｎ＝３～１;Ⅳ．〔Ｍ２（Ｏ２ＣＲ）ｎ〕＋,ｎ＝４～２。通过对该系列配合物质谱断裂过程的比较和分析,获得了配合物稳定性随金属离子及配体的变化如下：金属离子,Ｃｒ＞Ｍｎ＞Ｆｅ;桥配基,－ＣＨ３ＣＯ２＞－Ｃ２Ｈ５ＣＯ２＞－Ｃ６Ｈ５ＣＯ２;端配基,Ｐｙ＞Ｈ２Ｏ。本研究及先前的工作〔１,８〕还为某些三核铬,铁羧酸配合物在以乙炔加水或加氢为探针反应中存在活性物种：〔Ｃｒ３Ｏ（Ｏ２ＣＲ）３～４〕,〔Ｆｅ３Ｏ（Ｏ２ＣＲ）３〕和〔Ｆｅ３Ｏ－（Ｏ２ＣＲ）Ｏ〕～〔Ｆｅ３Ｏ４〕提供了佐证     

Homo- and heterometallic complexes based on polytopic carboxylic acid: synthesis,characterization, and property

Two heterometallic [K₄M₄(HL)₄(H₂O)₁₂] (M=Co (1), Ni (2)) and two homometallic [M₂L(H₂O)₇]?·?2H₂O ((M=Co (3), Ni (4)) (H₄L?=?(2-(bis(carboxymethyl)amino) terephthalic acid) have been synthesized and characterized by elemental analysis, FT-IR spectrum, and single-crystal X-ray diffraction. The isomorphous 1 and 2 contain K⁺ and M²⁺, in which K⁺ were bridged with M²⁺ through μ-HL^3? and μ-H₂O, leading to 2-D layer structures. The isomorphous 3 and 4 show homometallic binuclear complexes with μ-HL^3? as the bridging ligand. Various H-bonds including different H-bond helical chains form, by which 3 and 4 assemble into 3-D supramolecular frameworks. TG analysis indicates that the decomposition temperatures are [K₄M₄(HL)₄(H₂O)₁₂] (1)?>?[M₂L(H₂O)₇]?·?2H₂O (3)?>?H₄L.