2-氨基吡啶和多金属氧酸盐的两个新型配合物的合成，表征和性质研究

Two novel complexes based on 2-aminopyridine and polyoxometalates （POMs） formulated as （C5H7N2）6- [PMo11^ⅤMo^ⅥO40（V^ⅥO）4]·H2O （1） and （C5H7N2）16[P2W18O61.5]2 （2） were hydrothermally synthesized and structurally characterized by elemental analysis, ICP, IR, UV-Vis, TG, ESR and single crystal X-ray diffraction methods. Complex 1 consists of a novel tetra-capped Keggin POMs, [PMo11^ⅤMo^ⅥO40（V^ⅣO）4]^6-, in which four [V^ⅣO5] square pyramids cap the equatorial positions of Keggin core [PMo11^ⅤMo^ⅥO40]^14-, linked together with six protohated 2-aminopyridine via hydrogen bonding interactions. Dawson and lacunary Dawson POMs, [P2W18O62]^6- and [P2W17O61]^10- coexist in complex 2, they link together with sixteen protonated 2-aminopyridine via hydrogen bonding interactions. Complex 2 exhibits photochromic property.     

钨磷杂多酸盐的合成、表征及催化活性

合成了4个钨磷杂多酸盐——K10H2[P2W15Ti3O62]·2H2O,K12[P2W15(TiO2)3O59]·8H2O,K12[P2W15Zr3O62]·6H2O和K12[P2W15(ZrO2)3O59]·5H2O,用183WNMR,UV,IR,ICP和极谱-循环伏安等测试方法对其性质、结构进行了研究。结果表明它们都是具有Dawson结构的杂多配合物,对顺丁烯二酸的H2O2环氧化反应具有显著的催化活性。     

Synthesis,Characterization and Properties of TbIII and DyIII Coordination Compounds based on Isomeric Ligands

Reactions of the isomeric ligands Hpztza [Hpztza = 5‐(2‐pyrazinyl)tetrazole‐2‐acetic acid] and Hpmtza [Hpmtza = 5‐(2‐pyramidyl)tetrazole‐2‐acetic acid] with TbCl₃ · 6H₂O or DyCl₃ · 6H₂O under solvothermal conditions afforded four mononuclear complexes, [Ln(pztza)₂(H₂O)₆] · pztza · 3H₂O [Ln = Tb ( 1 ), Dy ( 2 )] and [Ln(pmtza)₂(H₂O)₆] · Cl · 3H₂O [Ln = Tb ( 3 ), Dy ( 4 )]. The compounds were characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. X‐ray diffraction analyses reveal that all structures are mononuclear. The four compounds are self‐assembled to form three‐dimensional networks by hydrogen bonds. The different positions of the nitrogen atom control the coordination mode of the ligands and further influence the crystal structures. Furthermore, the luminescence properties were also investigated at room temperature in the solid state.     

Syntheses, Structures and Coordination Behavior of Central Hydroxyl Group Containing Polydentate Ligands

Proteins containing dinuclear Cu (II), Zn (II) centers play paramount roles in biology1. As mimetic of metal-dependent esterase, dinuclear Cu (II) and Zn (II) complexes have received a great deal of attentions2~6. They are of interest in the field of biomimetic chemistry to provide an improved understanding of the function of the biological sites and as potential catalysts for substrate oxidations. Schiff base type polydentate ligands which contain centeral hydroxyl group have been wid…     

钼钨钒磷杂多酸稀土衍生物的合成、表征及催化性质

报道了通式为K     

过渡元素Dawson结构的钨钒磷四元杂多配合物的合成与表征

制备了两个系列１２种尚未见文献报道的过渡金属Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物。经元素分析和热重分析确定配合物通式为Ｋ９，１０［Ｐ２Ｍ（Ｈ２Ｏ）Ｗ１５Ｖ２Ｏ６１］．ｘＨ２Ｏ和Ｋ１０，，１１［Ｐ２Ｍ（Ｈ２Ｏ）Ｗ１４Ｖ３Ｏ６１］．ｘＨ２Ｏ）（Ｍ＝Ｆｅ＾３＾＋，Ｃｏ＾３＾＋，Ｎｉ＾２＾＋，Ｍｎ＾２＾＋，Ｃｕ＾２＾＋，Ｚｎ＾２＾＋＿），采用ＩＲ，ＵＶ，ＮＭＲ，ＥＳＲ和ＸＲＤ等方法进行了结构表征。     

含共轭三烯吡啶配体的配位聚合物的合成、结构及荧光性质

将1,6-双（4-吡啶基）-1,3,5-己三烯（bphte）和镉盐分别与2种羧酸配体（2,5-二呋喃二甲酸（2,5-H₂FDC）及1,3,5-均苯三甲酸（1,3,5-H₃BTC））进行溶剂热反应,得到2个配位聚合物：[Cd （2,5-FDC）（bphte）（H₂O）]_n （1）和[Cd （1,3,5-HBTC）（bphte）]_n （2）。对配合物1和2分别进行了元素分析、红外光谱、单晶X射线衍射、粉末X射线衍射和热重分析表征。配位聚合物1具有spl拓扑结构的三维互穿超分子框架,而配合物2是由bphte配体交叉连接一维链[Cd₂（1,3,5-HBTC）₂]_n形成的三维结构。配合物1和2在固态时表现出不同的荧光性质。配合物2遇到水溶液中Fe³⁺会发生荧光猝灭,因此以其作为荧光探针对水溶液中Fe³⁺进行了选择性荧光检测,它对Fe³⁺的检测限可达到0.013 μmol·L^-1。这种荧光猝灭过程可归因于Fe³⁺离子的吸收带与配合物2的激发带之间存在部分重叠。     

Synthesis and Structural Characterization of One‐Dimensional Cadmium(II) Coordination Polymers Containing Polydentate Nitrogen Ligands

The reactions of Cd(NO₃)₂·4H₂O with NH₄SCN and 2,4‐dpa (2,4‐dpa = 2,4‐dipyridineamine) in CH₃OH afforded the one‐dimensional coordination polymer [Cd(NCS)₂(2,4‐dpa)₂]_n, 1 , while reaction of Cd(NO₃)₂·4H₂O with NH₄SCN and PmPa (PmPa = 2‐(1‐piperazinyl)pyrimidine) in CH₃OH gave complex of the type [Cd(NCS)₂(PmPa)₂]_n, 2. Each of the 2,4‐dpa ligand in complex 1 is coordinated to the Cd²⁺ metal center through pyridyl nitrogen atoms to form the one‐dimensional chain structures. The distorted {CdN4S2} octahedral coordination geometry around Cd²⁺ center is completed by pairs of bidentate thiocyanato ligands. Complex 2 has the 1‐D arrangement constructed through one‐dimensional double μ(N,S) end‐to‐end bridging thiocyanato groups bridged Cd(II) chains interconnected through PmPa ligands.     

Three New Coordination Compounds with Neodymium Based on Tetrazole Containing Carboxylic Acid Ligands

Reactions of three tetrazole containing carboxylic acid ligands, namely, Hpztza, Htzpya, and Hpytza [Hpztza = 5‐(2‐pyrazinyl)tetrazole‐2‐acetic acid, Htzpya = 3‐(5‐tetrazolyl)pyridine‐1‐acetic acid, Hpytza = 5‐(3‐pyridyl)tetrazole‐2‐acetic acid] with NdCl₃ · 6H₂O under hydrothermal conditions, afforded the complexes [Nd(pztza)₂(H₂O)₆] · pztza · 3H₂O ( 1 ), [Nd₂(tzpya)₂(H₂O)₁₂]Cl₄ · 2H₂O ( 2 ), and [Nd(pytza)₂Cl(H₂O)₂] ( 3 ). The compounds were structurally characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. X‐ray diffraction analyses revealed that compound 1 displays a mononuclear structure, 2 shows a dinuclear structure, and 3 features a 1D polymeric chain structure via pytza as linker. Furthermore, the luminescent properties investigated at room temperature in the solid state show that compound 2 has an obvious decrease in its luminescence, when compared to the ligand.     

含氮和硫配位原子的配合物的合成和表征

近年来,对肼基二硫代甲酸酯衍生物的希夫碱配合物的研究已有不少报导,这是由于这类配体可与多种金属离子形成多种不同组成和立体结构的配合物以及已发现的抗癌,杀菌和抗病毒活性。其配体的抗菌活性可能是由     

含有甘氨酸的Keggin型杂多蓝的合成和抗艾滋病毒(HIV-1)活性研究

采用控制电位电解方法,制得8种含有甘氨酸的Keggin型钨系杂多蓝配合物．通过IR,UV-vis,^H NMR,^183W NMR,XPS等方法对其结构进行了表征．这类化合物具有较强的抗碱解能力．在MT4细胞内,对合成化合物进行了抗艾滋病毒(HIV-1)活性及毒性测定,发现该类化合物的抗艾滋病毒(HIV-1)活性随着还原电子数增多有增强的趋势,其中含有甘氨酸的十二钨锗酸4电子杂多蓝(代号HPBG-110)有较高的治疗指数(TI)．初步的试验结果表明：该类化合物的抗HIV-1活性作用是在病毒感染早期,通过抑制艾滋病毒(HIV-1)在靶细胞表面吸附而发挥作用的．     

Coordination Compounds of Alkali Metal Ions with Ligands Containing Phosphoryl Groups

Abstract

Ligands containing phosphoryl groups form coordination compounds with different metals. The coordination compounds of such ligands with alkali metal ions are considered. The effective charge of phosphorus atom in phosphoryl group is approximately + 1, and oxygen atom effective charge is approximately -1. Phosphorus and oxygen atoms effective charges depend on the nature of the substituents at phosphorus.     

钛钨杂多配合物的合成与表征

首次合成了杂多配合物K2[(C2H5)4N]2[TiW5O19].5H2O和K2[(C2H5)4N]2[(TiO2)W5O18].5H2O,配合物通过IR,UV,TG-DTA,摩尔电导,X射线粉末衍射进行了表征.结果表明[TiW5O19]4-具有L indqvist-Aronsson结构.     

Computation of the Number of Isomers of Coordination Compounds Containing Identical Monodentate Ligands and Chelating Ligands

This paper outlines a simple method of counting the number of isomers of coordination compounds containing identical monodentate ligands and chelating ligands.     

Synthesis and Characterization of Three Diverse Coordination Frameworks under Co-ligand Intervention

The chelating organic ligands of 2,2’-bipyridine (2,2’-bipy), di(pyrid-2-yl)amine (dpa) and 2,6-di(pyrid-2-ylamino)pyridine (dpap) were respectively applied to react with H2fum (fumaric acid) and copper salts, affording three different complexes [Cu2(fum)(2,2’-bipy)4]•2ClO4 (1), [Cu2(µ-OH)2(fum)(dpa)2]•2H2O (2) and [Cu(SO4)(H2O)(dpap)]•H2O (3). These complexes were determined by single-crystal X-ray diffraction. Each penta-coordinated Cu(II) ion exhibits a distorted trigonal bipyramidal geometry in 1. The fum ligand links copper ions to form a dinuclear copper unit. While in 2, the fum ligands connect [Cu2(µ-OH)2(dpa)2] unit to construct a 1D zigzag chain. Unexpectedly, when dpap instead of dpa was used under the same conditions, only one mononuclear complex 3 was formed. Crystal packings show that 1—3 form 3D supramolecular architectures through non-covalent interactions (multiple hydrogen bonds and C—H…π/π-π interactions). In addition, the study of the magnetic property reveals dominating ferromagnetic interactions between Cu(II) atoms in 1.     

Coordination Polymers with Bipyridyl Diene and Triene Ligands: Synthesis,Structures and Luminescent Properties

Solvothermal reactions of cadmium salts with bipyridyl diene and triene ligands[1,3-bis((E)-2-(pyridin-4-yl)vinyl)benzene-(1,3-bpeb) and 1,6-bis(4-pyridyl)-1,3,5-hexatriene(bphte)] and one bipyridyl triene ligand[1,6-bis(4-pyridyl)-1,3,5-hexatriene-(bphte)] in the presence of auxiliary carboxylic acids including 2,6-dichlorobenzoic acid(2,6-HDCBA) and 2-naphthal-enecarboxylic acid(2-HNCA) gave rise to four coordination polymers[Cd(bphte)(2,6-DCBA)₂]_n(1), {[Cd(bphte)(2-NCA)₂]·5.8H₂O}_n(2),[Cd₂(1,3-bpeb)₂(2,6-DCBA)₄]_n(3) and {[Cd₄(1,3-bpeb)₄(2-NCA)₇(HCOO)]·     

含羟基、膦酸根水溶性膦配体的合成

水溶性羟乙基膦配体;表征;含羟基、膦酸根水溶性膦配体的合成     

新型氮功能化大环配体的合成与表征

合成了新型氮功能化大环配体内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二乙酸乙酯(TETADE);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇,N＇,N＇＇,N＇＇＇-四乙酸乙酯(TETADE);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二乙酸(TETADA);内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇,N＇,N＇＇＇-四乙酸(TETATA)和内消旋-5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N,N＇-二异羟肟酸(TETAD-HA).均通过元素分析、IR,1H NMR和MS表征.     

半夹心结构含1,2-二硒碳硼烷的多核Co配合物的合成及结构表征

在氩气保护下,以邻位-碳硼烷、正丁基锂、硒粉和CpCo(CO)I2为起始原料,合成、分离得到配合物CpCo(Se2C2B10H10)(1)、(CpCo)2(Se2C2B10H10)(2)和(CpCo)4(μ3-Se)4Co2(μ3-Se2C2B10H10)4Co·CH2Cl2(3),并用元素分析、质谱、IR、1H NMR及X-射线单晶衍射对配合物(3)进行了表征。晶体属正交晶系,空间群P212121,其晶胞参数为:a=1.307 20(13)nm,b=1.391 37(11)nm,c=3.885 33(15)nm,β=90°,Z=4,V=7.066 6(9)nm3,μ=7.890 mm-1,Dc=2.138 g·cm-3,F(000)=4 268,R1=0.054 3,wR2=0.136 3。配合物中4个(Se2C2B10H10)2-配体和4个单硒基团形成了1个Co7Se12核。     

半夹心结构含1, 2-二硒碳硼烷的多核Co配合物的合成及结构表征

在氩气保护下,以邻位-碳硼烷、正丁基锂、硒粉和CpCo（CO）I₂为起始原料,合成、分离得到配合物CpCo（Se₂C₂B₁₀H₁₀）（1）、（CpCo）₂（Se₂C₂B₁₀H₁₀）（2）和（CpCo）₄（μ₃-Se）₄Co₂（μ₃-Se₂C₂B₁₀H₁₀）₄Co·CH₂Cl₂（3）,并用元素分析、质谱、IR、¹H NMR及X-射线单晶衍射对配合物（3）进行了表征。晶体属正交晶系,空间群P2₁2₁2₁,其晶胞参数为：a=1.30720（13）nm,b=1.39137（11）nm,c=3.88533（15）nm,β=90°,Z=4,V=7.0666（9）nm³,μ=7.890mm^-1,D_c=2.138g·cm^-3,F（000）=4268,R₁=0.0543,wR₂=0.1363。配合物中4个（Se₂C₂B₁₀H₁₀）^2-配体和4个单硒基团形成了1个Co₇Se₁₂核。