Salen型化合物的合成、表征及性质

设计合成了两种新型Salen配体H2L1(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二甲氧基-1,2-苯二胺)、H2L2(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二硝基-1,2-苯二胺)及相应的镍、铜、锌金属配合物ML1、ML2(M=Ni,Cu,Zn),并分别采用核磁共振(1HNMR)波谱、紫外-可见(UV-Vis)吸收光谱、红外(IR)光谱、质谱(MS)和元素分析进行了表征.探究了配体及其配合物的荧光性质.研究发现,与H2L1相比,配体H2L2由于引入强的吸电子基团―NO2,其荧光强度减弱.相对于配体,锌离子的配位则导致其配合物的荧光强度增强,而镍和铜离子的嵌入则使得配合物ML1、ML2(M=Ni,Cu)荧光猝灭.对电化学性质的研究表明,CuL1的氧化还原过程为准可逆的单电子过程;与H2L2相比,配体H2L1由于引入强的给电子基团―OCH3,其溶液的导电性降低.     

锌、镉配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了2个金属-有机配位聚合物[Zn(boba)(bix)]n(1)和[Cd(L1)(L2)]2n·nH2O(2)(H2boba=4,4′-(丁烷-1,2-二氧基)-二苯甲酸,bix=1,4-双(咪唑基-1-基)苯,H2L1=4-(羧基甲氧基)苯甲酸,L2=2-(4-羟基)-1H-咪唑并[4,5-f][1,10]菲咯啉)。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。     

锌、镉配位聚合物的合成、晶体结构及荧光性质（英文）

通过水热法合成了2个金属-有机配位聚合物[Zn(boba)(bix)]n(1)和[Cd(L1)(L2)]2n·nH2O(2)(H2boba=4,4′-(丁烷-1,2-二氧基)-二苯甲酸,bix=1,4-双(咪唑基-1-基)苯,H2L1=4-(羧基甲氧基)苯甲酸,L2=2-(4-羟基)-1H-咪唑并[4,5-f][1,10]菲咯啉)。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。配合物1为二维网状结构,配合物2为一维双链结构。此外,还研究了它们的荧光性质。     

含4,4'-联吡啶桥联的阳离子链和嘌呤-羧酸根抗衡阴离子的一维FeⅡ和CoⅡ聚合物,及由混合羧酸根配体构筑的二维EuⅢ聚合物的合成与表征

通过2′,3′-双脱氧肌苷和氯乙酸反应,得到1个多功能配体2-(6-oxo-6,9-dihydro-1H-purin-1-yl)acetic acid(HL)。该配体与其它附加配体一起与相应的金属盐反应,分别得到3个配位聚合物{[Fe(4,4′-bpy)(H2O)4](L′)2}n(1),{[Co(4,4′-bpy)(H2O)4](L′)2}n(2)和{[Eu(ox)0.5(su)(H2O)2]·H2O}n(3)(4,4′-bpy=4,4′-二联吡啶,ox=草酸盐,su=琥珀酸盐,L′=L的互变异构体2-(6-oxo-6,7-dihydro-1Hpurin-1-yl)acetate]。3个配合物均为单斜晶系C2/c空间群。配合物1和2为异质同构体,是由4,4′-二联吡啶桥联金属离子形成的一维链状结构,配合物3是由混合羧酸根构筑的二维框架结构。在配合物1和2中,脱质子的配体HL没有与金属离子配位,而是以互变异构体L′并通过氢键结合成二聚阴离子对[(L′)]2作为抗衡离子存在于配合物中。在配合物3中,配体HL分解为草酸根,2个EuⅢ被草酸根连接成二聚单元,这个二聚单元又被琥珀酸根连接成二维聚合物。另外还对配合物1和2的红外光谱、热分解性质以及配合物3的荧光性质进行了分析研究。     

含4,4′-联吡啶桥联的阳离子链和嘌呤-羧酸根抗衡阴离子的一维Fe~Ⅱ和Co~Ⅱ聚合物,及由混合羧酸根配体构筑的二维Eu~Ⅲ聚合物的合成与表征（英文）

通过2′,3′-双脱氧肌苷和氯乙酸反应,得到1个多功能配体2-(6-oxo-6,9-dihydro-1H-purin-1-yl)acetic acid(HL)。该配体与其它附加配体一起与相应的金属盐反应,分别得到3个配位聚合物{[Fe(4,4′-bpy)(H2O)4](L′)2}n(1),{[Co(4,4′-bpy)(H2O)4](L′)2}n(2)和{[Eu(ox)0.5(su)(H2O)2]·H2O}n(3)(4,4′-bpy=4,4′-二联吡啶,ox=草酸盐,su=琥珀酸盐,L′=L的互变异构体2-(6-oxo-6,7-dihydro-1Hpurin-1-yl)acetate]。3个配合物均为单斜晶系C2/c空间群。配合物1和2为异质同构体,是由4,4′-二联吡啶桥联金属离子形成的一维链状结构,配合物3是由混合羧酸根构筑的二维框架结构。在配合物1和2中,脱质子的配体HL没有与金属离子配位,而是以互变异构体L′并通过氢键结合成二聚阴离子对[(L′)]2作为抗衡离子存在于配合物中。在配合物3中,配体HL分解为草酸根,2个EuⅢ被草酸根连接成二聚单元,这个二聚单元又被琥珀酸根连接成二维聚合物。另外还对配合物1和2的红外光谱、热分解性质以及配合物3的荧光性质进行了分析研究。     

蝴蝶形单分子配合物的合成、晶体结构及其对水溶液中有害离子的检测

用苯并咪唑基配体5,5′-二(2-苯并咪唑基)-2,2′-联吡啶(H2L)与镍、锌离子溶剂热合成了配合物[Ni(HL)(HCOO)(H2O)](1)和[Zn(H2L)(H2O)2](NO3)2(2)。X射线单晶测试表明镍与锌配合物的晶体结构是只含一个配体和一个金属离子的蝴蝶形单分子。配合物分子之间存在大量分子间氢键,配合物1通过分子间氢键连接成了二维层状结构,配合物2通过分子间氢键连接成了三维超分子结构。配合物1和2在水溶液中很稳定,且能够微溶于水。荧光测试表明配合物2的固体及在水溶液中都具有很强的荧光性质,且能够在水溶液中高选择性、高灵敏度检测有害重金属离子Hg^2+及氧化性阴离子Cr2O7^2-。     

一种三维四元酸锰有机框架材料的合成、结构表征及荧光性能（英文）

通过水热法合成了一种结构新颖的金属有机框架物{[Mn(ttac)·(bibp)·H_2O]·[bibp]·H_2O}_n(其中H4ttac为4,5-二(3′-羧基苯基)-邻苯二甲酸,bibp为4,4′-联(咪唑基)联二苯).运用X射线单晶衍射、元素分析以及红外光谱对其进行了结构表征.结构测试表明该配合物通过一维链连接成二维层状结构,相邻的层之间存在游离的bibp分子,并且与已配位的bibp分子之间存在π…π堆积弱作用力进而构建成三维孔状结构,且该孔状结构中存在游离的水分子.此外,本文还研究了该配合物的荧光性质,荧光实验结果显示与配体相比,配合物的荧光发射波长发生蓝移.     

基于香豆素Schiff碱双核Ni（Ⅱ）和立方烷型Cu4（μ3-O）4的四核Cu（Ⅱ）配合物的合成、晶体结构及光谱性质（英文）

合成了2个3-氨基-4-羟基香豆素类Schiff碱双核Ni?髤和立方烷型Cu4(μ3-O)4的四核Cu?髤配合物,[Ni(L1)(DMF)(H2O)]2(1)(H2L1=3-((5-溴-2-羟基-亚苄基)-氨基)-4-羟基-苯并吡喃-2-酮)和[Cu4(L2)4]·DMF·CH3OH·2H2O(2)(H2L2=4-羟基-3-((2-羟基-3-甲氧基-亚苄基)-氨基)-苯并吡喃-2-酮),并通过元素分析、红外光谱、紫外光谱、荧光光谱及X射线单晶衍射分析等手段进行了表征。X射线单晶衍射分析结果表明:配合物1具有双核结构,由2个金属离子和2个配体单元组成,配合物2具有立方烷型Cu4(μ3-O)4的四核结构,由4个金属离子和4个配体单元组成。配合物1是单斜晶系、C2/c空间群;配合物2是四方晶系,I41/a空间群,且中心金属Ni?髤和Cu?髤离子的空间构型均为六配位的扭曲的八面体。此外,配合物1通过分子间氢键、C-H…π及π…π作用形成1D超分子链结构,配合物2通过分子内氢键和π…π作用形成3D超分子结构。此外,研究了H2L1,H2L2及其相应的Ni?髤和Cu?髤配合物的荧光性质。     

5-甲氧基-6′-羟基-2,2′-[乙二氧双(氮次甲基)]二酚及其四核锌(Ⅱ)配合物的合成与晶体结构(英文)

合成了一种不对称Salamo型配体5-甲氧基-6′-羟基-2,2′-[乙二氧双(氮次甲基)]二酚(H3L)及其四核锌髤配合物[Zn4L2(CH3OH)2(OAc)2],并通过X-射线单晶衍射分析确定了其晶体结构。其中配体呈现一种"V"构型,两个苯环单元的二面角为85.71(3)°,可近似认为是垂直的;而在配合物晶体结构中,金属离子有两种配位构型方式:一种为三角双锥构型,另一种为四方锥构型。配合物通过分子间的氢键作用形成了一个无限延伸的二维结构。     

同、异双核卟啉-Salen型金属配合物的合成及非线性光学性质

设计合成了两种新型卟啉-Salen型配体5-(3-氨基-4-(3,5-二叔丁基水杨醛基)-氨基苯基)-10,15,20-三苯基卟啉(1)和5-(N,N'-二(3,5-二叔丁基水杨醛基)-3,4-二氨基苯基)-10,15,20-三苯基卟啉(2)及其同、异双核金属配合物和单金属核配合物.采用氢核磁共振(1H NHR)谱、电喷雾质谱(ESI-MS)、傅里叶变换红外(FTIR)光谱和紫外-可见(UV-Vis)光谱等手段对各目标化合物进行了表征.用Z扫描技术研究了配体及其金属配合物的三阶非线性光学性质.实验结果表明:配体1和配体2具有相似的光学特征,均具有反饱和吸收的特性和自散焦效应;当不同的金属离子嵌入配体形成单、双核金属配合物后,分子的极性发生改变,他们的光学特性均受到影响.     

Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases

The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.     

Structural, magnetic, and electronic properties of phenolic oxime complexes of Cu and Ni

Square planar complexes of the type Ni(L(1))(2), Ni(L(2))(2), Cu(L(1))(2), and Cu(L(2))(2), where L(1)H = 2-hydroxy-5-t-octylacetophenone oxime and L(2)H = 2-hydroxy-5-n-propylacetophenone oxime, have been prepared and characterized by single-crystal X-ray diffraction, cyclic voltammetry, UV/vis spectroscopy, field-effect-transistor measurements, density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, and, in the case of the paramagnetic species, electron paramagnetic resonance (EPR) and magnetic susceptibility. Variation of alkyl groups on the ligand from t-octyl to n-propyl enabled electronic isolation of the complexes in the crystal structures of M(L(1))(2) contrasting with π-stacking interactions for M(L(2))(2) (M = Ni, Cu). This was evidenced by a one-dimensional antiferromagnetic chain for Cu(L(2))(2) but ideal paramagnetic behavior for Cu(L(1))(2) down to 1.8 K. Despite isostructural single crystal structures for M(L(2))(2), thin-film X-ray diffraction and scanning electron microscopy (SEM) revealed different morphologies depending on the metal and the deposition method (vapor or solution). The Cu complexes displayed limited electronic interaction between the central metal and the delocalized ligands, with more mixing in the case of Ni(II), as shown by electrochemistry and UV/vis spectroscopy. The complexes M(L(2))(2) showed poor charge transport in a field-effect transistor (FET) device despite the ability to form π-stacking structures, and this provides design insights for metal complexes to be used in conductive thin-film devices.     

Asymmetric Schiff Base (N 2 O 3 ) Complexes as Ligands Towards Mn(II), Fe(III) and Co(II), Synthesis and Characterization

Heterobi- and tri-nuclear complexes [LMM'Cl] and [(LM) 2 M'](M=Ni or Cu and M'=Mn, Fe or Co) have been synthesised. The heteronuclear complexes were prepared by stepwise reactions using two mononuclear Ni(II) and Cu(II) complexes of the general formula [HLM]·1/2H 2 O, as ligands towards the metal ions, Mn(II), Fe(III) and Co(II). The asymmetrical pentadentate (N 2 O 3 ) Schiff-base ligands used were prepared by condensing acetoacetylphenol and ethylenediamine, molar ratio 1 1, to yield a half-unit compound which was further condensed with either salicylaldehyde or naphthaldehyde to yield the ligands H 3 L 1 and H 3 L 2 which possess two dissimilar coordination sites, an inner four-coordinate N 2 O 2 donor set and an outer three-coordinated O 2 O set. 1 H NMR and IR spectra indicate that the Ni(II) and Cu(II) ions are bonded to the inner N 2 O 2 sites of the ligands leaving their outer O 2 O sites vacant for further coordination. Different types of products were obtained according to the type of metal ion. These products differ in stoichiometry according to the type of ligand in the parent compound. Electronic spectra and magnetic moments indicate that the structures of the parent Ni(II) and Cu(II) complexes are square-planar while the geometry around Fe(III), Mn(II) and Co(II) in their products are octahedral as elucidated from IR, UV-visible, ESR, 1 H NMR, mass spectrometry and magnetic moments.     

Optically active 4- and 5-coordinate transition metal complexes of bifurcated dipeptide Schiff bases

Symmetrical and unsymmetrical benzophenone Schiff bases of bifurcated dipeptides [e.g., Ar2C=N-CHR1- CONH-HNCO-CHR2-N=CAr2] have been synthesized using Boc methodology. These ligands may be regarded as chiral porphyrin mimics because of the alpha-carbons of the amino acids. The Schiff bases function as effective ligands for transition metals, particularly the late transition metals Ni(II), Cu(II), and Zn. Upon metal insertion, there is loss of the amide protons, resulting in N4 chelating ligands that retain the amino acid based chirality as well as newly generated metal-centered chirality, which for the Ni(II) complexes have been shown by X-ray analysis to be lambda (left-handed helix) if the amino acids are S. For Ni(II) and Cu(II), metal insertion results in highly colored complexes and is easily followed by UV-vis spectrophotometry. Several Ni(II) complexes were also characterized by 1H NMR. Co(II) and Mn(II) complexes were characterized by CW EPR. Two Cu(II) complexes, 7f.CuII and 7k.CuII, were characterized by EPR (ENDOR and ESEEM), which clearly showed the pentacoordinate nature of 7k.CuII.     

由醚氧桥连四羧酸配体构筑的锰(Ⅱ)和锌(Ⅱ)配位聚合物的合成、晶体结构、荧光及磁性质（英文）

采用水热方法,用醚氧桥连四羧酸配体(H4L)和菲咯啉(phen)、吡啶(py)分别与MnCl2·4H2O和ZnCl2反应,合成了2个二维配位聚合物{[Mn2(μ6-L)(phen)2]·5H2O}n(1)和{[Zn2(μ7-L)(py)]·H2O}n(2),并对其结构、荧光和磁性质进行了研究。结构分析结果表明2个配合物分别属于三斜和单斜晶系,P1和I2/a空间群。配合物1和2分别具有基于四核锰和双核锌的二维层结构。荧光和磁性研究结果表明,配合物2在室温下能发出蓝色荧光,聚合物1中相邻Mn?髤离子间存在反铁磁相互作用。     

First raw transition metal complexes of salicylidene and 2-hydroxy-1-naphthylidene-N-cyanoacetohydrazone

Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of salicylidene-N-cyano-acetohydrazone H2L1 and 2-hydroxy-l-naphthylidene-N-cyanoacetohydrazone H2L2 have been prepared in ethanolic solution and characterized by analytical, spectral, magnetic susceptibility, molar conductivity and TGA measurements. The analytical data show that all the complexes derived from H2L1 and H2L2 are formed in molar ratios 1M:2L, except the complexes of Mn(II), Co(II) and Cu(II) acetates of H2L2 and the complexes of Mn(II), Co(II) and Ni(II) acetates and CuCl2 of H2L1 are formed in 1:1 molar ratios. The conductance data show that all metal complexes are non-electrolytes. Electronic absorption spectra and magnetic susceptibility measurements proved that the prepared complexes have octahedral configuration except [Co(HL2)OAc] which has tetrahedral structure. The ligand field parameters were calculated for the Co(II) and Ni(II) complexes and the data show that the covalent character of the metal ligand sigma-bond is low. The ESR parameters of the Cu(II) complexes at room temperature were calculated. Thermal TGA for some solid complexes are reported.     

含5-氯水杨醛Schiff碱配体的镍和铜配合物的合成及晶体结构

合成了2个含三齿Schiff碱配体和单齿N-杂环分子的多核过渡金属配合物:1个含5-氯水杨醛缩对硝基苯甲酰腙(H2L1)和吗啡啉(Mf)的镍髤配合物[Ni(L1)(Mf)](1),1个含5-氯水杨醛缩水杨酰腙(H2L2)和吡啶(Py)的铜髤配合物[Cu2(L2)2(Py)2](2),并通过元素分析、红外光谱、紫外光谱以及单晶衍射等手段进行表征。在配合物1中,中心Ni髤与酰腙配体(L12-)的酚氧、亚胺氮、去质子酰胺氧原子以及中性吗啡啉氮原子配位形成平面四方形的N2O2配位构型,相邻配合物通过分子间氢键作用构筑成一维超分子链状结构。配合物2中含有2个晶体学上独立的双核铜髤配合物,相邻配合物分子的酚氧原子分别桥联2个[Cu(L2)(Py)]基本单元,形成2个含有Cu2(μ-O)2核心的配合物。每个Cu髤原子具有五配位的NONO(O)四角锥配位构型。     

Syntheses and Crystal Structures of Copper（Ⅱ） and Nickel Complexes with 1,2,3-Triazole-carboxylic Acid

Three novel complexes [Cu(L1)2(H2O)2] (1), [Ni(L1)2(H2O)2]·(H2O)4(2,HL1=5-methyl-1-(4-methylphenyl)-1,2,3-triazole-4-carboxylic acid) and [Ni2 (HL2)2(CH3OH)6]·(CH3OH)2(3,H3L2=1,2,3-triazole-4,5-dicarboxylic acid) were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1 and 2 are mononuclear structures, and are assembled into a two-dimensional sheet by C(7) H(7)···O(3) weak interactions or hydrogen-bonding interaction. Complex 3 is a centrosymmetric dinuclear structure, and is assembled into a three-dimensional supramolecular structure by hydrogen-bonding interaction.     

含末端炔基的Salen型金属配合物的合成、表征及性质

设计合成了新型含有末端炔基的Salen型配体H2Ln及其系列金属配合物MLn(n=1,2;M=Ni,Cu,Mn),并用氢核磁共振(1H NHR)谱、电喷雾质谱(ESI-MS)、元素分析(EA)、傅里叶变换红外(FT-IR)光谱和紫外-可见(UV-Vis)光谱等对各目标化合物进行了表征.采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.研究发现,配体除H2L1外均在测试范围内出现特征的亚胺氧化还原峰.镍和铜的配合物均经历了两个单电子的氧化还原过程;锰的配合物均出现由Mn(III)/Mn(II)产生的一对氧化还原峰,该过程为准可逆的单电子过程.H2Ln及MLn的溶液摩尔电导率数据显示,各目标化合物为弱电解质,具有一定的导电性.