多阴离子和铜磷酸盐为基元的杂化材料的合成、结构和性质

本文采用水热法合成了一个新的金属有机-无机杂化化合物 [Cu₄(phen)₄(HPO₄)₂(H₂O)₂(OH)₂][HPMo₁₂O₄₀]·H₂O (1) ( phen=邻菲咯啉)。通过元素分析、红外光谱、热重分析、X-射线单晶衍射对其进行了结构表征。化合物1是由四核铜磷酸盐、Keggin阴离子和晶格水分子组成。四核铜磷酸盐和多阴离子之间通过弱的M…O相互作用形成二维结构(M=Cu, Mo), 该二维结构通过氢键和π-π相互作用形成三维超分子框架,还对化合物1的电化学和电催化性质进行了研究。     

吡啶二羧酸修饰的稀土嵌入碲钨酸盐的合成及电化学生物识别性质

在乙酸钠水溶液中, 采用微波加热一步自组装策略合成了一系列罕见的2,6-吡啶二羧酸修饰的稀土嵌入Keggin型碲钨酸盐(PTEA)₇H₃K[RE₂(B-α-TeW₉O₃₃)₃W₃O₅(H₂O)₃(HDPA)]·22H₂O[RE=Ce³⁺(1), Pr³⁺(2), Nd³⁺(3), Sm³⁺(4); H₂DPA=2,6-吡啶二羧酸; PTEA=质子化的三乙醇胺]. 化合物1~4的聚阴离子由3个三缺位Keggin型 [B-α-TeW₉O₃₃]^8-构筑块通过1个{RE₂W₃O₅(H₂O)₃(HDPA)}¹³⁺异金属簇连接而成. 该异金属簇中, 2,6-吡啶二羧酸作为四齿配体与2个稀土离子(RE1和RE2)配位形成平面三杂环结构, 且RE1和RE2所在平面与W2, W2A, W16形成的平面互相垂直. 此外, 化合物1可与羧基化多壁碳纳米管(CMWCNT)复合形成1-CMWCNT复合材料. 该复合材料可以作为电极材料构建电化学生物传感器, 用于检测特定的DNA序列.     

一例夹心型含锰铋钨酸盐的合成、结构及磁学性质

在水相中合成了一例新的夹心型含锰铋钨酸盐Na₉H[（Mn （H₂O）₃）₂（Mn （H₂O）₂）（WO₂）（BiW₉O₃₃）₂]·30H₂O （1）。通过元素分析、紫外光谱、红外光谱、粉末X射线衍射、单晶X射线衍射和热重分析对其进行了结构表征。单晶结构分析表明化合物1中的阴离子是由2个三缺位Keggin型β-B-[BiW₉O₃₃]^9-阴离子内、外连接2个[（Mn （H₂O）₂）_0.5（WO₂）_0.5]²⁺配阳离子和2个[Mn （H₂O）₃]²⁺亚单元组成。磁学性质研究表明在化合物1中锰离子之间存在反铁磁耦合作用。     

一例含有八核钴簇的锗钨酸盐的合成、结构及性质

以K_8Na_2[A-α-Ge W_9O_(34)]·25H_2O,Co(NO_3)_2·6H_2O和K_2CO_3等为原料,利用常规水溶液法合成了一例基于三缺位Keggin型多金属氧簇{Ge W_9O_(34)}的高核过渡金属衍生物K_(10.5)Cs_4H_(1.5){[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}·12H_2O(1),并通过红外光谱、元素分析、热重分析和X射线单晶衍射等分析手段对其进行了表征。化合物1含有一个V型的多酸阴离子簇{[Co_8(OH)_6(H_2O)_2](CO_3)_3(Ge W_9O_(34))_2}~(16-),该阴离子进一步通过K~+和Cs~+离子连接形成二维结构。磁学性质研究表明,化合物1中Co~(2+)离子之间主要为反铁磁性耦合。     

以PW9为结构基元构筑的夹心型多金属氧酸盐化合物的合成与晶体结构

通过水热合成方法合成了以夹心多酸阴离子{Ni₄(H₂O)₂(PW₉O₃₄)₂}^10-,乙二胺(en)和Ni(Ⅱ)构筑的夹心型多金属氧酸盐化合物[Ni(en)₂]₂[{Ni(en)₂}{Ni(en)₂H₂O}₂{(PW₉O₃₄)₂Ni₄(H₂O)₂}]·16H₂O(1),采用IR、单晶X-射线衍射法、TG/DTG及循环伏安法对标题化合物进行结构和性质研究。该化合物的夹心多酸阴离子通过[Ni(en)₂]²⁺连接形成一维链,并进一步通过氢键作用形成3D超分子结构。     

以PW9为结构基元构筑的夹心型多金属氧酸盐化合物的合成与晶体结构

通过水热合成方法合成了以夹心多酸阴离子{Ni₄(H₂O)₂(PW₉O₃₄)₂}^10-,乙二胺(en)和Ni(Ⅱ)构筑的夹心型多金属氧酸盐化合物[Ni(en)₂]₂[{Ni(en)₂}{Ni(en)₂H₂O}₂{(PW₉O₃₄)₂Ni₄(H₂O)₂}]·16H₂O(1),采用IR、单晶X-射线衍射法、TG/DTG及循环伏安法对标题化合物进行结构和性质研究。该化合物的夹心多酸阴离子通过[Ni(en)₂]²⁺连接形成一维链,并进一步通过氢键作用形成3D超分子结构。     

两种钴离子支撑钼磷多金属氧酸盐的水热合成及晶体结构

利用水热技术合成了2个新型钴支撑的磷钼多金属氧酸盐超分子化合物:(C2N2H10)5[(P4Mo6O25(OH)6)2Co](1)和(Co(H2O)6)2(C5NH6)6[(P4Mo6O25(OH)6)2Co]·10H2O(2).并通过元素分析、红外光谱、热重分析和X射线单晶衍射对2个化合物进行了表征.结果表明:化合物1属于三斜晶系,P-1空间群;晶胞参数a=1.179 9(2)nm,b=1.337 7(2)nm,c=1.479 7(3)nm,α=73.435(2)°,β=74.383(2)°,γ=66.499(2)°,V=2.020 5(6)nm3,F(000)=1 327,Z=1;化合物2属于属于三斜晶系,P-1空间群;晶胞参数a=1.220 68(11)nm,b=1.381 08(13)nm,c=1.687 18(15)nm,α=92.275(1)°,β=104.774(1)°,γ=114.475(1)°,V=2.468 8(4)nm3,F(000)=1 649,Z=1.     

二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质

以二苯乙醇酸为配体合成了1个新的化合物[Cu(2,2′-bipy)(BAA)][Cu(2,2′-bipy)(BAA)(H2O)]2.(H2O)3(BAA=二苯乙醇酸阴离子,2,2′-bipy=2,2′-联吡啶)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.121 7(5)nm,b=1.360 2(6)nm,c=2.335 2(10)nm,α=99.260(6)°,β=101.223(8)°,γ=94.805(8)°,V=3.425(3)nm3,Dc=1.385 g.cm-3,Z=6,μ(Mo Kα)=0.992 mm-1,F(000)=1 474,最终偏离因子R1=0.0561,wR2=0.1128。在标题化合物的不对称单元中有3个单核铜(Ⅱ)配合物,且3个中心铜(Ⅱ)离子的配位数不完全相同,如Cu(1)离子的配位数是4,而Cu(2)和Cu(3)离子的配位数都是5。本文还测定了标题化合物的电化学性能和荧光性能,结果表明:在电化学过程中配合物的电子转移是准可逆的,电子转移数为2个;配合物在478 nm的光激发下可发射荧光。     

铜二取代三元杂多化合物的制备、晶体结构和性质

The half Dawson structure complex has been prepared by reaction of Na₂WO₄·2H₂O, Na₂MoO₄·2H₂O and NaH₂PO₄ in water. [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] have been synthesized by reaction of [PW₅Mo₄O₃₄]^9- and Cu²⁺ in water and recrystallized in a mixed acetone/water solvent. They were characterized by elemental analyses, IR spectra and electronic spectra. The crystal structure of [TBA]₄H₃[PW₆Mo₄Cu₂O₃₈(H₂O)₂] has been determined by X-ray structure analysis for the first time, which belongs to trigonal with space group R-3, a=b=c=1.53081 (18) nm, α=β=γ=109.458(17)°, Z=1, D_c=3.141Mg·m^-3, R=0.0780, R_w=0.1480. The sites of the molybdenum, tungsten and copper atoms are disordered over 12 possible locations in the crystal, and the anion has a high symmetry due to the disorder of the molybdenum, tungsten and copper atoms. CCDC: 176656.     

含磷钼酸及2,2’-联吡啶-3,3’-二羧酸配体的铜配位聚合物的合成、晶体结构与电化学性质

在水热条件下合成了一个新的化合物{[Cu₄(PMo₁₂O₄₀)(H₂O)₅(H₂bpdc)(Hbpdc)(bpdc)₂]·6H₂O}_n(H₂bpdc=2, 2’-联吡啶-3, 3’-二羧酸), 并用元素分析、IR、TG和X-射线衍射等手段进行了表征。结果表明本化合物的晶体结构中, 最小不对称单元包含1个 [Cu₄(H₂O)₅(H₂bpdc)(Hbpdc)(bpdc)₂]³⁺阳离子, 1个[PMo₁₂O₄₀]^3-阴离子和6个结晶水分子。Cu(Ⅱ)与相邻[PMo₁₂O₄₀]^3-的桥氧原子配位, 形成一维链状结构。电化学研究表明, 化合物存在三步氧化还原过程。     

Synthesis,Electrocatalytic Properties and Crystal Structure of a New Organic—Inorganic Hybrid Constructed from Dodecamolybdophosphoric Acid and Benzotriazole

IntroductionIn the last few years there has been a rapidlygrowing number of reports in the literature ad-dressing the use of polyoxometalate- based hybridmaterials as catalysts,non- linear optical materialsand anti- virus drugs[1— 5] . In all the cases men-tioned above,the size,the shape and the chargesof the inorganic counter anions strongly affect theproperties of the materials. Polyoxometalates arelarge in size and high in electron accepting abili-ty[6] .They can form novel compounds with …     

铌取代型杂多钨酸盐的合成、表征、生物活性及晶体结构

合成了铌、过氧化铌取代的钨硅、钨锗杂多配合物M     

两个新的双二茂铁硫脲衍生物FcL1和FcL2的合成、结构及电化学性质

以二茂铁苯甲酰氯和二茂铁间(对)苯胺为原料,合成了两个新的双二茂铁硫脲衍生物FcL₁和FcL₂.通过IR,¹HNMR和元素分析等手段确定了标题化合物的结构.X射线单晶结构分析表明,FcL₁属于三斜晶系,P1空间群,R₁=0.0786,wR=0.1762.电化学分析结果表明,FcL₁和FcL₂的电化学性质相似,说明化合物中的两个二茂铁基所处的化学环境基本相同.间苯胺取代和对苯胺取代对化合物在电极表面的扩散系数影响不大,但对其反应速率常数则有较大的影响.     

Hydrothermal Synthesis,Crystal Structure,and Thermal Stability of Two New Metal Phosphonates with a Pillared Layered Structure

Two new metal phosphonates with a 3D pillared layered framework based on N,N′‐piperazinebis(methylenephosphonic acid), H₂O₃PCH₂NC₄H₈NCH₂PO₃H₂ (H₄L), Sn[O₃PCH₂NHC₄H₈NHCH₂PO₃] ( 1 ) and Pb₃(OH)₂[O₃PCH₂NC₄H₈NCH₂PO₃] ( 2 ), have been synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. For compound 1 , each ψ‐square pyramidal SnO₄ unit is in turn corner‐shared by four CPO₃ tetrahedral from four different phosphonate ligands to form two‐dimensional inorganic puckered layers in ab planes. In compound 2 , the complicated inorganic layer (bc planes) is built up of ψ‐PbO₄N, PbO₆ and CPO₃ polyhedra. The overall structure for two compounds may be described in terms of alternating inorganic infinite layers and organic pillars {CH₂N(C₂H₄)₂NCH₂}, to form a 3D pillared layered structure.     

Synthesis, Crystal Structure and Electrochemistry of Two Complexes(YLn)3+[PW12O40]3-(L=Me2SO, Me2NCHO)

The reaction of a-H3[PWi2O40]with Y(NO3)3 in the presence of DMF or DMSO leads to two complexes complex 1 consists of discrete [YLn]3 cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2,donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.     

大环多胺配体BDBPH的设计合成及其晶体结构

用Pb(SN)₂作模板,2,6-二甲酰基对甲苯酚与二亚乙基三胺通过[2+2]缩合反应,经NaBH₄还原、脱Pb²⁺、酸化等操作,得晶体BDBPH·6HBr·4H₂O.晶体属单斜晶系,P2_1/c空间群,晶体学参数:a=1.4441(5)nm,b=1.1482(4)nm,c=1.2090(6)nm,α=90°,β=96.92°,γ=90°,V=1.9900nm³大环分子采取椅式构型,6个Br-和4个H₂O分子对称分布于大环两侧.该大环配体结构新颖,可用于多种金属配合物的研究,对进一步了解金属酶活性中心的结构及其催化作用机理具有重要价值.     

Hydrothermal Synthesis,Crystal Structure,and Characterization of Two New Metal Diphosphonates with a 3D Pillared Layered Structure

Two new metal diphosphonates with a 3D pillared layered framework, [Zn₂L] · 2H₂O ( 1 ) and [Sb(HL)(H₂O)] · H₂O ( 2 ) (H₄L = H₂O₃PCH₂NC₄H₈NCH₂PO₃H₂), were synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction as well as IR spectroscopy, elemental analyses, and thermogravimetric analyses. For compound 1 , each ZnO₃N tetrahedron is in turn corner‐sharing through three CPO₃ tetrahedra from three different phosphonate ligands to form two‐dimensional inorganic layers in the ab plane. In compound 2 , the inorganic puckered layers are composed of pseudo‐octahedral bipyramidal SbO₅ and CPO₃ tetrahedra in the bc plane. The overall structure of both compounds may be described in terms of alternating inorganic infinite layers and organic pillars{–CH₂N(C₂H₄)₂NCH₂–} to form a 3D pillared layered structure.     

Synthesis,Crystal Structure,and Characterization of three New Letrozole Complexes

Three new letrozole complexes {[Cu(Le)₄Cl₂] · (H₂O)} ( 1 ), {[Ni(Le)₄Cl₂] · (H₂O)}( 2 ) and {[Co(Le)₄Cl₂] · (H₂O)} ( 3 ) (Le = letrozole = 1‐[bis(4‐cyanophenyl)methyl]‐1, 2, 4‐triazole) were obtained from self‐assembly of CuCl₂, NiCl₂ · 6H₂O, and CoCl₂ · 6H₂O with medicine letrozole. All compounds were characterized by IR spectroscopy, elemental, single‐crystal as well as powder X‐ray diffraction, and thermogravimetric analyses. The analyses of the structures indicate that all crystals belong to monoclinic system, space group C2/c, for complex 1 with crystal data a = 34.501(18) Å, b = 12.724(7) Å, c = 16.116(9) Å, β = 114.958(7) °, V = 6414(6) Å ³, Z = 4, F(000) = 2660, R₁ = 0.0668, wR₂ = 0.1574; for complex 2 , a = 34.769(6) Å, b = 12.7267(18) Å, c = 16.046(2) Å, β = 115.281(3) °, V = 6420.1(16) Å ³, Z = 4, F(000) = 2656, R₁ = 0.0510, wR₂ = 0.0896; for complex 3 , a = 35.063(8) Å,b = 12.658(3) Å, c = 16.056(4) Å, β = 115.387(3) °, V = 6438(2) ų, Z = 4, F(000) = 2652, R₁ = 0.0528, wR₂ = 0.1205. The local arrangements around central metal atoms (Cu^II, Ni^II, and Co^II) can be best described as distorted octahedra which are constructed by two chlorine atoms and four monodentate nitrogen atoms from different letrozole ligands. XRD results of 1 – 3 show that all peaks displayed in the measured patterns at room temperature closely match those in the simulated patterns generated from single‐crystal diffraction data, indicating single phases of 1 – 3 were formed.     

Synthesis, Crystal Structure and Biological Activity of a Novel Amino Acid Salt (HGly)_4[HPMo_(12)O_(40) ]_2·22H_2O

IntroductionIn the last few years there has been a rapidlygrowing number of reports in the literature ad-dressing the use of polyoxometalates as antiviraland anti- tumor agents[1— 4] . Polyoxometalates areexcellent molecular acceptors,a number of organicsubstrates containing N,S and O atoms are excel-lent molecular donors,by means of molecular as-semblies,they can form novel compounds at roomtemperature[5— 7] .As is known,amino acids are thebasic units of biological molecules and interactio…     

Synthesis,Crystal Structure and Electrochemistry of Two Complexes （YLn）3＋[PW12O40]3-（L=Me2SO,Me2NCHO）

The reaction of α-H3[PW12O40] with Y（NO3）3 in the presence of DMF or DMSO leads to two complexes with the formulae {Y（DMSO）7}·PW12O40（1） and {[Y（DMF）7]2PW12O40}·PW12O40（2）. The crystal structures indicate that complex 1 consists of discrete [YLn]3＋ cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2, donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.