5-(5-氟-2-吡啶偶氮)-2,4-二氨基甲苯与钴显色反应的研究及应用

研究了新合成试剂5-(5-氟-2-吡啶偶氮)-2,4-二氨基甲苯(5-F-PADAT)与钴(Ⅱ)的显色反应。实验表明,在pH4.7~9.0范围内,钴与试剂形成紫红色配合物,其最大吸收波长位于506 nm。该配合物在无机酸作用下,可转化为另一具有较高吸收特性的质子化型体,最大吸收波长红移到565 nm,适宜的酸浓度范围分别为:0.24~3.6 mol/L HClO4、0.16~3.84 mol/L H2SO4、0.48~2.4 mol/L HCl、0.64~3.84 mol/L H3PO4。配合物表观摩尔吸光系数ε565=9.1×104L.mol-1.cm-1,钴(Ⅱ)质量浓度在0~0.5μg/mL内符合比尔定律。所拟方法已应用于维生素B12针剂中微量钴的测定。     

新显色剂1-偶氮苯-3-(5-氰基-2-吡啶)-三氮烯的合成及其与镉的显色反应

报道了新显色剂1-偶氮苯-3-(5-氰基-2-吡啶)-三氮烯的合成及其与镉的显色反应。在表面活性剂OP存在下,pH 11.0的Na2B4O7-NaOH缓冲溶液中,该试剂与镉发生显色反应,生成4∶1型的红色配合物。配合物的最大吸收峰位于525 nm,表观摩尔吸光系数为2.02×105L.mol-1.cm-1。Cd2+的线性范围为1~0.6μg/mL。用拟定方法测定废水中微量镉,结果令人满意。     

1-(4-硝基苯)-3-(3-甲基吡啶)-三氮烯的合成及其与锌的显色反应

报道了显色剂1-(4-硝基苯)-3-(3-甲基吡啶)-三氮烯的合成及其与锌的显色反应研究。在Triton X-100存在下,pH 11.0的硼砂-氢氧化钠缓冲溶液中,该试剂能与锌发生显色反应,锌与显色剂形成摩尔比为1∶4的黄色配合物,在445 nm波长处有最大正吸收峰,在535 nm波长处有最大负吸收。以445 nm为参比波长,535 nm为测量波长进行双波长测定,表观摩尔吸光系数为1.88×105L.mol-1.cm-1,锌浓度在0~12μg/25 mL范围内符合比耳定律。用拟定方法测定植物样品中微量锌,分析结果的相对标准偏差均小于2.5%,加标回收率在99.6%~100.4%之间。     

1-偶氮苯-3-(5,6-二甲基-1,2,4-三氮唑)-三氮烯与镉的显色反应及其应用

报道了新显色剂1-偶氮苯-3-(5,6-二甲基-1,2,4-三氮唑)-三氮烯(ABDMTT)的合成及其与镉的显色反应。在OP表面活性剂存在下,pH 11.0的Na2B4O7-NaOH缓冲溶液中,该试剂能与镉生成2∶1型的红色配合物。配合物的最大吸收峰位于525 nm,表观摩尔吸光系数为2.04×105L.mol-1.cm-1。镉的质量浓度在0~0.60 mg/L范围内符合比尔定律。用拟定方法测定废水中微量镉,结果满意。     

锌-精氨酸配合物极谱吸附波的研究

在乙醇胺 -盐酸溶液 ( p H9.5)中 ,锌 -精氨酸配合物在单扫示波极谱上于 -1 .2 7V( vs.SCE)产生灵敏吸附波。可用于 1 .0× 1 0 - 7～ 3 .0× 1 0 - 6 mol/L 范围内锌含量的测定 ,利用该波测定了人发和废水中锌的含量。该波为 1∶ 1锌 -精氨酸配合物在电极上吸附还原而产生。     

1-偶氮苯-3-(5-溴-2-吡啶)-三氮烯与锌(Ⅱ)的显色反应及其应用

合成了 1 偶氮苯 3 (5 溴 2 吡啶 ) 三氮烯 (ABBPDT) ,研究了ABBPDT与锌 (Ⅱ )的显色反应。在pH =11.0的Na2 B4O7-NaOH缓冲溶液中 ,TritonTX - 10 0表面活性剂存在下 ,ABBPDT与锌 (Ⅱ )生成 4∶1的红色配合物。配合物的最大吸收峰位于 5 30nm ,表观摩尔吸光系数为 1.36× 10 5L/ (mol·cm)。锌 (Ⅱ )的浓度在 0～ 15 .0 μ犂/ (2 5mL)范围内符合比耳定律。用该方法测定人发中的微量锌 ,平均回收率 (n =6 )为 98.8%～ 99.5 % ,RSD为 1.6 %～ 1.9%。     

5-(5-碘-2-吡啶偶氮)-2,4-二氨基甲苯分光光度法测定微量钌(Ⅱ)

研究了新合成试剂5-(5-碘-2-吡啶偶氮)-2,4-二氨基甲苯(5-I-PADAT)与钌(Ⅱ)的显色反应。实验表明,在30%乙醇存在下于pH 4.0~6.2 HAc-NaAc缓冲介质中,钌(Ⅱ)与5-I-PADAT形成稳定的配合物,其最大吸收波长位于529 nm。该配合物在无机酸(HCl,H2SO4,HClO4,H3PO4)作用下,可转变为另一种具有较高吸收特性的配合物,其最大吸收波长位于509 nm,适宜的酸浓度范围分别为0.15~0.60 mol/L HCl,0.15~0.48 mol/L H2SO4,0.15~0.48 mol/LHClO4和0.15~0.90 mol/L H3PO4。表观摩尔吸光系数5ε09=5.72×104L.mol-1.cm-1,钌含量在0~0.5μg/mL内符合比尔定律。40倍的银、10倍的锇、6倍的金和4倍的Pt、Rh、Ir等贵金属离子不干扰钌的测定,钯的干扰可利用其与钌(Ⅱ)显色温度和酸度的差异性消除。方法可用于催化剂中微量钌的测定。     

4''-对二甲氨基苯基-2,2'':6'',2"-三联吡啶-锌配合物在含水乙醇介质中对磷酸根离子的高选择性识别研究

合成了一种-2,2':6',2"-三联吡啶衍生物,4'-对二甲氨基苯基-2,2':6',2"-三联吡啶(L),利用L与锌离子形成的稳定配合物(ZnL),用紫外可见吸收光谱和荧光光谱研究了在无水乙醇和含水乙醇介质中各种阴离子对该配合物ZnL的吸收光谱和荧光发射光谱的影响.发现该配合物能存含水乙醇介质中选择性的识别磷酸根类离子.磷酸根、磷酸氢根与磷酸二氢根离子分别与ZnL配合物以1:1、2:1及2:1结合模式影响体系的吸收和荧光发射,ZnL配合物对磷酸根类离子的识别作用主要源于配合物多余的结合位点.     

4′-对二甲氨基苯基-2,2′∶6′,2″-三联吡啶-锌配合物在含水乙醇介质中对磷酸根离子的高选择性识别研究

合成了一种-2,2′∶6′,2″-三联吡啶衍生物,4′-对二甲氨基苯基-2,2′∶6′,2″-三联吡啶(L),利用L与锌离子形成的稳定配合物(ZnL),用紫外可见吸收光谱和荧光光谱研究了在无水乙醇和含水乙醇介质中各种阴离子对该配合物ZnL的吸收光谱和荧光发射光谱的影响,发现该配合物能在含水乙醇介质中选择性的识别磷酸根类离子。磷酸根、磷酸氢根与磷酸二氢根离子分别与ZnL配合物以1∶1、2∶1及2∶1结合模式影响体系的吸收和荧光发射,ZnL配合物对磷酸根类离子的识别作用主要源于配合物多余的结合位点。     

2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺的合成及其与铑(Ⅲ)的高灵敏显色反应的研究

合成了新显色剂2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺(5-I-PADMA),并研究了其与铑(Ⅲ)的显色反应。结果表明,在pH4.0~6.2的乙酸-乙酸钠缓冲介质中,铑(Ⅲ)与5-I-PADMA可形成稳定的1∶2配合物,该配合物呈现2个吸收峰,分别位于557、597 nm处。配合物形成后,以适量HClO4(0.24~5.57 mol.L-1)酸化,可转变为另一种具有较高吸收特性的质子化形体,其吸收峰分别红移至564、613 nm处。表观摩尔吸光系数达ε613=1.86×105L.mol-1.cm-1,铑的质量浓度在0~0.56 mg.L-1范围内符合比尔定律。该法是目前测定痕量铑的高灵敏显色体系之一,且具有良好的选择性。所建立的方法操作简单,应用于催化剂中微量铑的测定,结果满意。     

二{桥-2，4，6-三[二(2-吡啶基)胺]-1，3，5-三嗪-N，N′，N ″，N′′′}·四氯合二锌(Ⅱ)的合成与晶体结构(英)

A dinuclear Zn(Ⅱ) complex C₆₆H₄₈Cl₄N₂₄Zn₂·2CH₃OH·2H₂O (1) was synthesized and characterized by X-ray crystallography. In the complex, two 2,4,6-tris[bis(2-pyridyl)amino]-1,3,5-triazine ligands are bridged together by two zinc(Ⅱ) ions and stacked in a parallel manner. CCDC: 267649.     

Synthesis and Crystal Structure of 3,3''-Bis(2-benzimidazolyl)-2,2''-dipyridine with Hydrated Zinc(Ⅱ) Perchlorate

The reaction of Zn(ClO4)2·6H2O with 3,3'-bis(2-benzimidazolyl)-2,2'-dipyridine (L) gave a mononuclear zinc(Ⅱ) complex: [ZnL2](ClO4)2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, 1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal (C54H54Cl2N14O14Zn, Mr=1259.38) belongs to the monoclinic system, space group C2/c with a=20.874(2), b=14.9953(16), c=20.462(3) (A), β=101.553(2)°, V=6274.8(13) (A)3, Z=4, Dc=1.333 g/cm3, F (000)=2608, μ(MoKα)=0.548 mm-1, R=0.0682 and Wr=0.1931 for 4984 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The Zn(Ⅱ) is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2 cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.     

含1,2二取代的苯并咪唑配体的Zn(Ⅱ)络合物上化学固定CO2转化为环状碳酸酯

合成了一种新的Zn(Ⅱ)配合物ZnCl2(L1)2] (1) (L1为 2-(2-噻吩)-1-(2-噻吩甲基)-1H-苯并咪唑),并采用NMR和IR光谱、元素分析、ESI-HRMS光谱测定和热重分析等对它进行了表征,其分子结构也由单晶X射线衍射确定.络合物1含有单核四面体Zn(Ⅱ)单元,即所谓的锁定的几何结构,这源自分子中存在弱的分子间S···π和π-π配体间相互作用.通过简易的合成路线即可制得苯并咪唑配体及其与Zn(Ⅱ)配合物.采用CO2与环氧化物耦合生成环状碳酸酯反应考察了1的催化活性,以及反应条件的影响.该配合物在无溶剂条件下可高效催化多种环氧化物的转化,具有较好的转化率,TONs和TOFs.     

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.     

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。     

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(Ⅱ) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc(Ⅱ) complexes, [Zn2L2aCl4]·2[ZnL(CH3OH)Cl2] 1 and [ZnL2(NO3)2] 2,were synthesized by reacting ZnX2·nH2O (X = Cl-, NO3-) and a Schiff base ligand 2-[(4-me-thylphenylimino)methyl]-6-methoxyphenol (C15H15NO2, L) which was obtained by the condensation of o-vanillin (2-hydroxy-3-methoxybenzaldehyde) with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis,1H-NMR spectra and thermogravimetric analysis. The Schiff base ligand and its zinc(Ⅱ) complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli,Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.     

Synthesis and Luminescence Properties of Three High-dimensional Coordination Polymers:Zn(Ⅱ) with Imidazole or Benzimidazole Ligand

A novel 2D coordination polymer [Zn2(bim)4]n(1)(Hbim=benzimidazole) based on dihydrated-[N,N'-bis(2-aminophenl)-oxalamide](L1·2H2O) with zinc nitrate has been synthesized.Previously we have synthe-sized complexes [In2Zn3(im)12]n(2)(Him= imidazole) and [Zn(im)2]n(3) successfully.In complex 1,each Zn(Ⅱ) coor-dinated with four ligands adopts a distorted tetrahedron coordination mode,and the 2D grid structure is built by the Zn(bim)4 as the secondary building unit(SBU).The luminescence properties of the three c...     

L-苯丙氨酸与大环锌配合物的手性拆分、晶体结构与单点能计算

外消旋大环锌配合物［Zn(rac-L)］(ClO₄)₂(L=5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷)与L-苯丙氨酸(L-Phe)在弱碱性条件下反应制得单手性配合物［Zn(RR-L)(L-Phe)］(ClO₄)(2),其结构经IR,元素分析,圆二色光谱和X-射线单晶衍射表征。2（CCDC: 1 491 999）属四方晶系,空间群P4₁,晶胞参数a=12.647(11) , b=12.647(11) , c=18.295(3) , β=90 °, V=2 926.2(6) ³, Dc=1.393 g·cm^-3, Z=4, μ=0.977 mm^-1, R₁=0.040 7, wR₂=0.081 5。     

二齿肼基硫代甲酸苄酯席夫碱锌配合物的合成、晶体结构和抗肿瘤活性

以2,4-二氯苯甲醛缩肼基二硫代甲酸对氯苄酯为配体与锌盐反应合成了配合物Zn(L)2,L=2,4-二氯苯甲醛缩肼基二硫代甲酸对氯苄酯阴离子。通过元素分析和红外光谱对配合物进行了表征,并用X-射线单晶衍射测定了配合物的单晶结构。配合物属于单斜晶系,P21/n空间群,a=1.242 6(10)nm,b=1.024 4(11)nm,c=2.840 2(2)nm,β=101.740 0(10)°,Mr=842.81,V=3.539 7(5)nm3,Z=4,μ=1.412 mm-1,Dc=1.582 g.cm-3,F(000)=1 696,R1=0.039 0,wR2=0.086 2(观察衍射点)和R1=0.164 0,wR2=0.099 6(全部衍射点),Final GooF=1.015。在配合物的晶体结构中,中心锌离子与2个二齿席夫碱配体中的2个硫原子和2个氮原子形成四配位四面体构型。抗肿瘤活性实验采用了MTT比色法,初步研究表明配合物对人胃癌细胞增殖具有明显的抑制作用。     

一个双核锌(Ⅱ)配合物[Zn2(L)2(Mf)2]的合成、结构、热稳定性及荧光性质

The binuclear Zn(Ⅱ) complex [Zn2(L)2(Mf)2] with 2-hydroxyacetophenone benzoylhydrazone (H2L) and monodentate N-heterocycle, morphine (Mf) has been synthesized and characterized by elemental analysis, IR, UV, molar conductivity, TG and X-ray diffraction structural analysis. Crystal data: monoclinic, space group P21/n with 0=1.263 9(6) nm, b=1.085 2(4) nm, c=1.313 4(5) nm, β=92.16(2)°, V=1.800(l) nm3, Z=2, 0C=1.493 g·cm-3,μ= 1.388 mm-1, F(000)=840, and final R =0.038 4, wR =0.087 9. The two Zn(Ⅱ) centers in the centrosymmetric binuclear complex are bridged by phenolic oxygen atoms with Zn…Zn separation of 0.3150(1) nm. The coordination geometry of each Zn(Ⅱ) atom is trigonal bipyramidal. The fluorescence activities of ligand and the complex were also studied. CCDC: 712643.