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。     

Salen型铜(Ⅱ)和镍(Ⅱ)配合物的合成与电化学性质

合成了2种salen型配体及其具有N2O2配位模式的salen型铜、镍金属配合物ML1和ML2[M=Cu,Ni;salen型配体L1=N,N'-双(4-羟基-邻羟苯亚甲基)-2,2'-联苯二胺;L2=N,N'-双(3,5-二叔丁基-邻羟苯亚甲基)-2,2'-联苯二胺];并通过核磁共振波谱(1H NMR)、电喷雾质谱(ESI-MS)、红外光谱(FT-IR)、紫外-可见光谱(UV-Vis)和元素分析等对配体及目标金属配合物进行了表征。循环伏安法电化学研究发现,在-1.5~+1.5 V电势扫描中,CuL2和NiL1只有一组单电子准可逆氧化还原过程,而NiL2发生了两次氧化还原反应。     

N-(2-氧乙酸-3-甲氧基)苄叉二胺合锌(Ⅱ)配合物的合成、晶体结构及光学性质研究

本文通过修饰邻香草醛芳环上羟基的方法,得到两种Schiff碱配体:N,N′-二(2-氧乙酸-3-甲氧基)苄叉乙二胺(H2L1)和N,N′-二(2-氧乙酸-3-甲氧基)苄叉1,3-丙二胺(H2L2),利用水热合成方法以新合成的配体为基点设计合成了2个新的六配位Schiff碱锌(Ⅱ)配合物[Zn(L1)]·7H2O(1)和[Zn(L2)]·7H2O(2),通过元素分析、红外光谱和核磁共振光谱等测试手段对配合物进行了表征,并用X射线单晶衍射测得Zn(Ⅱ)配合物的晶体结构。X射线晶体学研究表明两种配合物晶体结构中都包含多个溶剂水分子,配合物1是以Zn(Ⅱ)为中心扭曲的三方棱柱构型,配合物2是以Zn(Ⅱ)为中心扭曲的八面体构型。初步研究了两种配合物的固体发光性,结果表明这两种配合物具有良好的光致发光的性能,有望在光学材料方面得到应用。     

两个单核镍含氮配体配合物的合成、晶体结构及荧光性质(英文)

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni(phen)2(H2O)2](1,6-nds)·2H2O(1)和[Ni(phen)3](1,6-nds)·10H2O(2)(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni(phen)2(H2O)2]2+阳离子。2个没有配位的水分子通过氢键与[Ni(phen)2(H2O)2]2+和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni(phen)3]2+阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438 nm。     

类Salen和β-二酮稀土配合物的晶体结构和荧光性质（英文）

通过1,3-苯二胺缩邻香兰素和Ln(acac)3·H2O(Ln=Ce,Eu)反应,合成了2种双核稀土配合物[Ce2L(acac)4(CH3OH)]2·2CH2Cl2(1)和[Eu2L(acac)4(CH3OH)]2·2CH2Cl2(2)。X射线单晶衍射分析确定了配合物的晶体结构,配合物中2个稀土离子均为8配位,具有相同的反四棱柱的配位构型。荧光性质研究表明配合物2显示稀土离子和配体共发光,主要原因是配体1,3-苯二胺缩邻香兰素的三线态能级与中心离子Eu(Ⅲ)的三线态能级相匹配。     

新的稀土Eu,Tb(Ⅲ)β-二酮三元配合物的合成与光谱性质

采用Claisen缩合反应合成了一种β-二酮1-(4-氨基苯)-3-苯基丙烷-1,3-二酮(L:C15H13NO2),以元素分析和1H NMR谱确定了其组成,核磁和红外分析结果表明L主要以烯醇式存在。以L为第一配体,分别以邻菲罗啉(phen),2,2’-联吡啶(bipy)为第二配体,合成了新的稀土Eu,Tb(Ⅲ)三元配合物。通过元素分析、红外光谱、紫外光谱、磷光光谱和荧光光谱对合成的配合物进行了表征。荧光光谱表明:稀土铽配合物的发光性能优于稀土铕配合物,进一步研究表明配体L与Tb3+间能级差较匹配,分子内传能效率高;phen对配合物的荧光敏化效果优于bipy,表明第二配体的刚性和共轭性越大,配合物的发光性能越好。     

吡啶-2,6-二甲酸衍生物及其Tb(Ⅲ)和Eu(Ⅲ)配合物的合成与荧光性质

以吡啶-2,6-二甲酸(DPA)为起始物,合成了4-羟甲基吡啶-2,6-二甲酸(4-HMDPA)和4-(N,N-二羧甲基氨基)亚甲基吡啶-2,6-二甲酸(4-BMDPA)两种新型多功能配体,并制备了DPA,4-HMDPA及4-BMDPA的Tb(Ⅲ)和Eu(Ⅲ)配合物,对配合物的固体和溶液态的荧光性质进行了研究. 结果表明,在吡啶4位引入弱吸电子基团4-羟甲基会减弱稀土配合物的荧光强度; 在水溶液中稀土配合物与溶液的pH值有着密切的关联,中性水溶液中荧光强度较大; 分子偶极矩较小的溶剂中稀土配合物荧光强度较强. 表明4-BMDPA是较理想的稀土荧光敏化剂.     

一个双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O的合成、晶体结构和性质

双核金属配合物对于生物化学和磁化学都是非常重要的.在本文中,1,2,3-三氮唑-4,5-二羧酸(H3tda)配体和硝酸镍在常温常压下反应得到了1个三氮唑桥联的双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O(1),并通过元素分析、红外光谱、X-射线单晶衍射、热重分析以及超导量子干涉仪(SQUlD)对其晶体结构和磁、热性质进行了表征.晶体数据表明该配合物属三斜晶系,空间群为P(1).在配合物1中,2个1,2,3-三氮唑-4,5-二援酸配体利用2个相邻的氮原子桥联2个金属镍离子形成一个双桥的双核镍配合物.这些双核镍单元又通过体系中存在的大量的氢键相互作用形成了三维超分子骨架.磁性分析显示双核镍单元内镍镍之间存在反铁磁相互作用.     

3,4-二甲氧基苯乙酸邻菲哕啉镱(Ⅲ)配合物的合成、晶体结构及荧光光谱

合成了 3,4-二甲氧基苯乙酸邻菲啰啉镱(Ⅲ)配合物(C84H82Yb2N4O24):[Yb2(DMPA)6(phen)2](HDMPA=3,4-二甲氧基苯乙酸(C12H12O4),phen=1,10-邻菲哕啉)(CCDC:757541),并通过元素分析、红外(IR)光谱、热重分析(TG-DTG)对其进行了表征,用单晶X射线衍射测定了配合物的晶体结构.配合物C84H82Yb2N4O24属三斜晶系,空间群P(-1),品胞参数:a=1.22877(14)nm,b=1.23235(16)nm,c=1.45234(19)nm,α=91.726(7)°,β=103.321(7)°,γ=113.885(6)°,品胞体积:V=1.9379(4)nm3,品胞内分子数Z=1,相对分子质量M,=1877.62,电子数F(000)=946,密度Dc=1.609 g·cm-3,吸收系数μ(Mo Kα)=2.481 mm-1.测定了铕和铽掺杂(2.5%,5.0%,10.0%,摩尔分数)的配合物的荧光光谱,结果表明,单独的配体没有荧光,在形成配合物后,依然显示铕(Ⅲ)离子和铽(Ⅲ)离子的特征发射峰,这表明配体将吸收的能量有效地转移给了中心离子,配体起到了很好的敏化作用.     

对甲酰基苯甲酸金刚烷酯席夫碱及其镍(Ⅱ)配合物的合成、表征及性质研究

以金刚烷醇、4-甲酰苯甲酸和邻氨基苯酚、邻氨基苯硫酚、邻溴苯胺为原料合成了三种不同的对甲酰基苯甲酸金刚烷酯席夫碱及其镍(Ⅱ)配合物(H1、H2、H3),利用红外光谱、紫外-可见光谱、核磁共振氢谱对其进行结构表征。同时通过荧光光谱、热重分析和电化学分析对席夫碱及其镍(Ⅱ)配合物的荧光性质、热稳定性、电化学性质进行研究,结果表明,镍(Ⅱ)配合物H1、H2和H3均具有良好的荧光性质,且H1、H2具有较高的电化学活性。     

基于一维[H_2Mo_4O_(14)]_n~(2n-)链和双吡啶双酰胺配体的三维锌配合物的合成、结构与性能

选择柔性的双吡啶双酰胺配体N,N'-双(3-吡啶甲酰胺基)-1,2-乙烷(3-bpye)、钼酸铵和氯化锌在水热条件下自组装制备了一个基于一维[H_2Mo_4O_(14)]_n~(2n-)链的三维锌配合物[Zn(3-bpye)(H_2Mo_4O_(14))(H_2O)_2],并通过元素分析、红外光谱、热重分析等技术手段研究了配合物的结构,并利用X射线单晶衍射分析进行了晶体结构表征。结构解析揭示标题配合物是三斜晶系,P-1空间群,晶胞参数a=0.61310(3)nm,b=1.04750(6)nm,c=1.06540(6)nm,α=78.5540(10)°,β=77.5350(10)°,γ=89.9050(10)°,V=0.65420(6)nm~3,M_r=981.47,D_c=2.491 g/cm~3,Z=1,F(000)=468,R_1=0.0290,ωR_2=0.1068。标题配合物中,金属锌离子连接一维[H_2Mo_4O_(14)]_n~(2n-)链形成一种二维无机双金属层[Zn(H_2Mo_4O_(14))]_n,相邻的层间又通过双齿配体3-bpye连接形成三维CdSO_4拓扑的骨架结构。配合物表现出强的荧光发射特性,而且其在紫外光照下对亚甲基蓝和罗丹明B均有明显的催化降解活性。     

Zn(II) complexes with pyridine derived N6 and N8 donor azamacrocyclic ligands

A novel N6 macrocyclic ligand, L¹ (2,8,14,20-tetramethyl-3,7,15,19,25,26-hexaaza-tricyclo[19.3.1.1^9,13]hexacosa-1(24),9,11,13(26),21(25),22-hexaene), was obtained by reduction of the 2 + 2 condensation product of 2,6-diacetylpyridine and propane-1,3-diamine. Zinc(II) complexes of L¹, of a related N8 macrocycle, L³ (3,6,9,17,20,23,29,30-octaaza-tricyclo[23.3.1.1[11,15]]triaconta-1(28),1,13,15(30),25(29),26-hexaene), similarly prepared by 2 + 2 condensation of 2,6-diformylpyridine and diethylenetriamine and of a tetra N-2-cyanoethyl derivative of a homologue of L¹ prepared from diformyl pyridine and ethane-1,2-diamine, L² (3-[6,14,17-tris-(2-cyano-ethyl)-3,6,14,17,23,24-hexaaza-tricyclo[17.3.1.1^8,12] tetracosa-1(23),8(24),9,11,19,21-hexaen-3-yl]-propionitrile), were prepared. Structures were determined for [ZnL¹](ClO₄)₂ · H₂O, [ZnL²](NO₃)₂ and [Zn₂L³(NO₃)₂](NO₃)₂ · H₂O. The [ZnL¹](ClO₄)₂ · H₂O and [ZnL²](NO₃)₂ complexes present a mononuclear endomacrocyclic structure with the metal in an octahedral distorted environment coordinated by the six donor nitrogen atoms from the macrocyclic backbone while the complex [Zn₂L³(NO₃)₂](NO₃)₂ · H₂O is dinuclear with both metal atoms into the macrocyclic cavity coordinated by four donor nitrogen atoms from the macrocyclic framework and one oxygen atom from one monodentate nitrate anion, in a distorted square pyramidal arrangement.     

Syntheses and Supramolecular Structures of Two Nickel(Ⅱ) Compounds Based on Two Thiosemicarbazone Ligands

Two new compounds, [Ni₂(L¹)(Py)₆]Py·CH₃OH(1) and [Ni₃(L²)₂(Py)₄]·2DMF(2)(H₄L¹=N,N'-bisalicyl- bisthiocarbamide; H₃L²=3-hydroxyl-2-naphthalene thiosemicarbazide; Py=pyridine; DMF=dimethyl fumarate), based upon two thiosemicarbazone ligands have been obtained and characterized by elemental analysis, Fourier transform infrared(FTIR) and X-ray diffraction(XRD). Compound 1 possesses a binuclear cluster, in which the bisalicylbisthiocarbamide acts as a hexadentate bridge. Compound 2 exhibits a linear trinuclear cluster with the triply-deprotonated ligand acting as pentadentate bridge. C―H···O, C―H···π and C―H···S weak interactions further link these molecules to form interesting supramolecular networks.     

Synthesis, crystal structures and catalytic oxidation of aromatic hydrocarbons by oxovanadium(V) complexes of aminebis(phenolate) ligands

The coordination chemistry of two aminebis(phenolate) ligands (H₂L¹ and H₂L²) around vanadium(V) is described. Vanadium(V) oxo complexes (1, 2 and 3) of all the ligands were obtained readily by the reaction between the ligand precursors and [VO(acac)₂]. Single crystal X-ray structure analysis showed that all of the complexes are penta-coordinated with trigonal bipyramidal geometry in NO₄ coordination environment. The tripodal nitrogen atom of the respective ligands and monodentate alkoxo group occupy apical positions. These complexes structurally resemble very closely to the active sites of vanadium haloperoxidases (VHPO) and were found to catalyze the oxidation of toluene to benzoic acid and isomers of xylene to the corresponding hydroxy acids with turn over numbers ranging between 134 and 188. Based on mass spectra the mechanism of the catalytic process was proposed to proceed through the formation of hydroxo–hydroperoxo intermediate, which is different from halo peroxidase reactions.     

Ligation properties of 2-acetyl-2-thiazoline semicarbazone (ATsc): Isolation, spectroscopic and X-ray study of ATsc and its Cu(II) and Ni(II) complexes

A new ligand, 2-acetyl-2-thiazoline semicarbazone (ATsc), has been prepared and characterized by a variety of physico-chemical techniques. Likewise, the metal complexes [CuCl₂(ATsc)] and [Ni(ATsc)₂](NO₃)₂ · H₂O have been isolated and characterized through elemental analysis, IR, UV–Vis–NIR diffuse reflectance and magnetic susceptibility, as well as, in the case of the copper complex, by means of EPR. Moreover, the structures have been determined by X-ray diffraction. In both complexes the Schiff base acts as a tridentate ligand through N(1), N(2) and O atoms, making two five-membered chelate rings. The copper complex consists of monomeric molecules in which the copper atom is five coordinated in a distorted square-pyramidal geometry, with one ATsc and two chlorine ligands. The complex cation of nickel possesses approximately a non-crystallographic C₂ symmetry. The environment around the nickel atom may be described as a distorted octahedral geometry with the metallic atom coordinated to two ATsc ligands.     

镓-水杨基荧光酮伏安络合吸附波的研究

在pH为3.0的0.2mol/L邻苯二甲酸氢钾-HCI和5.0×10^-6mol/L水杨基荧光酮底液中,线性扫描可得灵敏的Ga-SAF络合物吸附波,峰电位为-0.93V(vsSCE).镓在7.5×10^-9～3.8×10^-7mol/L浓度范围内与峰高成正比关系.     

New Supramolecular Networks Based on Paratungstate with N-Donor Bridging Ligands

Three new supramolecular networks based on paratungstate and N-donor bridging ligands, [H₂bpmp]_2.5H[H₂W₁₂O₄₀]2H₂O(1), [H₂(bpp)]₂[H(py―CH₃)]_0.25[H(py―C₂H₅)]_0.25H_1.5[H₂W₁₂O₄₀]·4H₂O(2) and [H₂pip]₃[H₂W₁₂O₄₀](3)[bpmp=N,N'-bis(4-pyridylmethyl)piperazine; bpp=1,3-bis(4-pyridyl)propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared(IR), thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD). All the compounds show high-dimen- sional supramolecular networks based on [H₂W₁₂O₄₀]^6- and the protonated N-donor ligands via the N―H···O―W hydrogen bonds and/or π···π stacking interactions. Their luminescent properties were investigated.     

Four Coordination Polymers Assembled with a New Biscarboxyl-functionalized Schiff Base Ligand

Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H₄L), four polymers,[(CH₃)₂NH₂]₂·[Mn₃(L)₂(H₂O)₄]·2DMF(CP1),[Fe₂(L)(H₂O)(DMF)](CP2),[(CH₃)₂NH₂]·[Cu(HL)]·H₂O(CP3) and[Ni₂(L)(teta)]·2DMF·H₂O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N₂O₂] pocket and the external carboxylate groups of L^4- anion are ligated by Mn²⁺ ions, and the structure displays a layer. In CP2, the Fe²⁺ cations are linked by L^4- anions to form a binuclear double chain. CP3 displays a[Cu₂(HL)₂] dimer. In CP4, the Ni²⁺ ions are connected by L^4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.     

Syntheses,Crystal Structures and Luminescent Properties of Three New Gallium Complexes Containing Pyridine-2,6-dicarboxylic Acid

Three new gallium complexes formulated as [Ga(PDA)₂][Ga(H₂O)(PDA)(phen)]·4H₂O(1), [Ga(PDA)₂]· (H₂IN)·2H₂O(2) and [Ga(OH)(PDA)(H₂O)]₂(3)(H₂PDA=pyridine-2,6-dicarboxylic acid; phen=1,10-phenanthroline; HIN=isonicotinic acid) have been synthesized under hydrothermal conditions. In the mixed-ligand system of complex 1, PDA^2? and phen are connected to the central Ga³⁺ cation as tri- and bi-dentate ligands, respectively. In complex 2, each Ga³⁺ cation is six-coordinated by two PDA^2? anions octahedrally. Complex 3 shows a binuclear structure, with the bond distance of Ga1-Ga2 being 0.30061(3) nm. The 3D supramolecular structures of the three complexes are constructed via hydrogen bonds and aromatic π-π packing interactions. All the three complexes exhibit intense blue emission at room temperature in the solid state, which are attributed to π^*-π transition centered on the ligands.     

Crystal structure and luminescence property of ternary terbium p-aminobenzoic acid complexes with different second ligands

Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL₃(DMSO)(H₂O)]₂ (1), [TbL₃(DMF)(H₂O)]₂ (2) and [TbL₃(Bpy)(H₂O)]₂·2H₂O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L⁻ ligand and the characteristics of a second ligand, are discussed.