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1.
在溶剂热条件下,以H6P2Mo18O62、对苯二甲酸(H2BDC)、4,4'-联吡啶(Bipy)和硝酸锌为原料构筑了1个三维金属有机骨架复合材料H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5),并采用红外光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)、N2吸附-脱附等手段对产物进行了表征.同时,研究了产物对水溶液中亚甲基蓝(MB)的吸附性能,并探讨了MB初始p H值、初始浓度和温度对吸附量的影响.结果表明,产物的等温吸附模型符合Langmuir等温吸附模型,动力学符合拟二级动力学.H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5)对亚甲基蓝的吸附是自发和放热的,此外,产物对甲基紫、罗丹明B、孔雀石绿等阳离子染料也具有良好的吸附性能.  相似文献   

2.
黄妙龄 《无机化学学报》2014,30(7):1694-1700
利用对乙酰氨基苯甲酸(HPABA)和邻菲咯啉(phen)、硝酸铜在DMF/CH3OH/H2O溶液中合成了单核铜配合物[Cu(PABA)(phen)(H2O)2]·(NO3)·H2O(1),然后又和4,4′-联吡啶(4,4′-bpy)、硝酸锌在DMF/CH3OH/H2O溶液中获得配位聚合物{[Zn(PABA)2(4,4′-bpy)]·4H2O}n(2)。根据X射线衍射分析结果,配合物1中每个铜离子周围有2个氮原子和3个氧原子与之配位形成畸变的四方锥配位构型,然而在配合物2中,六配位八面体构型的锌离子通过配体4,4′-联吡啶扩展为一维Zigzag型链。分别对这两个配合物的热稳定性和电化学性质进行了研究。  相似文献   

3.
以氯甲基化交联聚苯乙烯树脂(CMCPS)为载体和大分子引发剂,1-乙烯基咪唑(VIM)为单体,溴化亚铜/2,2'-联吡啶为催化剂体系,采用表面引发原子转移自由基聚合技术(SI-ATRP),将1-乙烯基咪唑接枝到CMCPS树脂表面,制得新型咪唑型螯合树脂(VIM-CMCPS),并采用X射线光电子能谱、元素分析和扫描电镜对其进行表征。考察了该螯合树脂对Cd2+和Zn2+的吸附性能、动力学和热力学参数。该螯合树脂表面VIM接枝密度达1.008 mg/m2。结果表明,该树脂对Cd2+和Zn2+的吸附量随溶液初始浓度和温度的升高而增加,当p H值分别为3.6和2.4时,对Cd2+和Zn2+的吸附效果最佳,树脂的静态饱和吸附容量分别为653.1 mg/g和793.3 mg/g,Langmuir和Freundlich方程均呈现良好的拟合度。热力学平衡方程计算得ΔG0,ΔH=24.47 k J/mol,ΔS0,表明该吸附过程是自发、吸热、熵增加的过程。动力学研究表明,该过程符合准二级动力学模型。  相似文献   

4.
合成了一维分子梯状配合物{[Cu2(4,4'-bpy)3(p-Ab)2(H2O)2]·(NO3) 2·4H2O}n(4,4'-bpy=4,4'-联吡啶,p-Ab-=对氨基苯甲酸根离子),该配合物晶体属单斜晶系,P2(1)/c空间群,晶胞参数:a=1.110 7(5) nm,b=1.550 4(3) nm,c=1.450 9(3) nm,β=104.81(3)°,V=2.415 5(12) nm3,Z=2.铜离子周围有3个氧原子和3个氮原子与之配位,其中2个氧原子由对氨基苯甲酸的螯合氧原子提供,另一个氧原子由配位水提供,3个氮原子分别由三个4,4'-联吡啶提供.这六个原子在铜离子周围形成一个畸变的八面体配位环境.配体对氨基苯甲酸只有一种配位形式--双齿螯合,第二配体4,4'-联吡啶的两个氮原子均参与配位,将配合物组装成一维分子梯结构.  相似文献   

5.
碘化亚铜和4,4′-二联吡啶在溶液中反应的二种方法可制备出标题化合物的2个不同红色晶体,结构表征出两种晶体分别是单斜C2/c(1)和四方I41/acd(2)空间群。在[Cu(μ-I)(μ-4,4-bipy)]n结构中,铜原子是处于与2个碘原子和2个相互扭曲4,4′-二联吡啶中的氮原子的扭曲四面体配位环境中,2个[Cu(μ-I)]2单元和2个桥式4,4′-二联吡啶配体形成1个[Cu2(μ-I)2(μ-4,4-bipy)]2直角单元,4个直角单元经4个4,4′-二联吡啶侧式桥联而形成1个大的八角环,并由此与直角单元相互垂直而形成1个二维框架结构。  相似文献   

6.
在中温混合溶剂热条件下合成了两个金属铜配位聚合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2和Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(bipy=联吡啶,C8H4O4=1,3-间苯二甲酸),并对其进行了单晶结构解析及相关性能表征.配合物Cu3(2,2′-bipy)2(C8H4O4)2(C8H5O4)2(1)晶体属三斜晶系,P1空间群,a=1.03314(4)nm,b=1.08350(3)nm,c=1.15826(4)nm,α=83.104(2)°,β=84.609(2)°,γ=66.125(2)°,Z=1.配合物Cu(Ⅰ)Cu(Ⅱ)(4,4′-bipy)1.5(C8H4O4)(C8H5O4)(2)晶体属三斜晶系,P1空间群,a=1.06979(3)nm,b=1.09209(3)nm,c=1.47887(3)nm,α=91.795(2)°,β=93.2460(10)°,γ=118.6170(10)°,Z=2.通过使用不同的有机碱配体(2,2′-联吡啶和4,4′-联吡啶),并调节不同有机碱配体的用量,得到了结构不同的两个目标晶体产物相.产物均可稳定到3...  相似文献   

7.
利用水热法合成了新型一维配合物Cu(pico)(4,4′-bipy)(H2O)ClO4·H2O(1,bipy=联吡啶,pico=邻吡啶甲酸根),其结构经IR,元素分析和X-射线单晶衍射表征.1属于单斜晶系,P21/n空间群,晶胞参数:a=0.853 57(8)nm,b=1.610 58(14)nm,c=1.416 85(13)nm,β=99.407(2)°,V=1.921 6(3)nm3,Z=4,Mr=477.31 g·mol-1,Dc=1.650 g·cm-3,μ=1.326mm-1,F(000)=972,R1=0.078 1,wR2=0.239 1,S=1.102.1中Cu2 与邻吡啶甲酸配体上一个N原子和一个O原子、两个4,4′-联吡啶的N原子以及一个水分子的O原子配位,形成了四方锥配位几何构型.在a c轴方向,Cu2 与两个4,4′-联吡啶分子经桥联作用形成一维zig-zag链;链与链通过氢键形成三维结构.  相似文献   

8.
用硫酸钴、4,4'-联吡啶和2-磺酸基乙基膦酸合成了一个新颖的钴化合物:[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4,并对其进行了红外.元素分析、热重测试,通过单晶衍射仪测定了其晶体结构.结果表明,配合物属单斜晶系C2/c空间群,分子式为C_(22)H_(45)Co_2N_4O_(22)PS_2,分子量为930.57,晶胞参数为a=19.8456(18),b=11.2957(10),c=34.719(3)(A),β=106.095(3)°,晶胞体积为7477.9(12)(A)~3,Z=8,Dc=1.653 g/cm~3,F(000)=3856,μ=1.131 mm~(-1),最终残差因子R_1=0.0726,wR_2= 0.1719(相对于5612个I>2σ(I)的可观测衍射点).在这个化合物中,二齿配体4,4'-联吡啶把Co(II)桥连成[Co(4,4'-bipy)]~(2+)链.化合物中的[Co(4,4'-bipy)]~(2+)链有三个不同的朝向.2-磺酸基乙基膦酸没有参与配位而是做为一个有机模板剂填充在[Co(4,4'-bipy)]~(2+)链形成的空隙中.  相似文献   

9.
以银离子、3,3 ',4,4'-二苯硫酮四羧酸阴离子(tdpc)和4,4'-联吡啶(bipy),合成了一种新型化合物[十二水合(3,3',4,4'-二苯硫酮四羧酸)(4,4'-联吡啶)水合银][ Ag2 (tdpc)(bipy)2][ Ag2 (bipy)2 (H2O)]·12H2O,该化合物为链状结构,Ag…Ag相互...  相似文献   

10.
报道了一个由μ-1, 3-N3-和4,4′-联吡啶桥联的配合物{Mn(4,4′bpy)(N3)2}n的合成、晶体结构和磁性. 该配合物具有罕见的脚手架状的三维结构, 磁性测量表明配合物具有弱的反铁磁性J(N3-) = -5.74 cm-1, J(4,4′bpy) = -0.72 cm-1. 同时还报道了其衍生物({Ni(4,4′bpy)(N3)2}n, {Cu(4,4′bpy)(N3)2}n, {Fe(4,4′bpy)(N3)2}n)的合成和表征.  相似文献   

11.
The compounds (π-C5H5)(CO)2LM-X (L = CO, PR3; M = Mo, W; X = BF4, PF6, AsF6, SbF6) react with H2S, p-MeC6H4SH, Ph2S and Ph2SO(L′) to give ionic complexes [(π-C5H5)(CO)2LML′]+ X. Also sulfur-bridged complexes, [(π-C5H5)(CO)3W---SH---W(CO)3(π-C5H5)]+ AsF6 and [(π-C5H5)(CO)3M-μ-S2C=NCH2Ph-M(CO)3(π-C5H5)], have been obtained. Reactions with SO2 and CS2 have been examined.  相似文献   

12.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO)3(CH3CN)2(Cl)(SnRCl2)] (R = Ph, Me) with P(4-XC6H4)3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO)2(CH3COCH3)2(PPh3)(Cl)(SnRCl2)]·nCH3COCH3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO)3{P(4-XC6H4)3}(μ-Cl)(SnRCl2)]2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO)3(CH3CN) {P(4-XC6H4)3}(Cl)(SnRCl2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes.  相似文献   

13.
The ruthenium(II) complex Ru(CO)2(NH2(NH2CH2C6H5)2(Si(C6H5)(CH3)2)I has been prepared by the reaction of Ru(CO)4(Si(C6H5)(CH3)2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO)2(NH2CH2C6H5)2(Si(C6H5)(CH3)2)I·1/3C5H12 (triclinic; P ; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest.  相似文献   

14.
The compound [RU332- -ampy)(μ3η12-PhC=CHPh)(CO)6(PPh3)2] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU3(η-H)(μ32- ampy) (μ,η12-PhC=CHPh)(CO)7(PPh3)] with triphenylphosphine at room temperature. However, the reaction of [RU3(μ-H)(μ3, η2 -ampy)(CO)7(PPh3)2] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU332-ampy)(μ,η 12 -PhC=CHPh)(μ,-PPh2)(Ph)(CO)5(PPh3)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H2), although progressive deactivation of the catalytic species is observed. The dihydride [RU3(μ-H)232-ampy)(μ,η12- PhC=CHPh)(CO)5(PPh3)2] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction.  相似文献   

15.
The hierarchical metal-organic frameworks(MOFs),such as Y(BTC)(H_2O)_6,are prepared with yttrium nitrate and benzene-1,3,5-tricarboxylic acid at room temperature.The product is characterized by Fourier transform infrared(FT-IR),X-ray diffraction(XRD),scanning electron microscopy(SEM)and thermogravimetric analysis(TGA).The Y(BTC)(H_2O)_6 particles are sufficiently rigid for performing solid phase extraction and they exhibit favorable selectivity toward the adsorption of hemoglobin.The adsorption behavior of hemoglobin onto the Y(BTC)(H_2O)_6 fits the Langmuir adsorption model with a theoretical adsorption capacity of 555.6 mg g 1.An adsorption efficiency of 87.7%for 100μg mL 1hemoglobin in 1 mL sample solution(at pH 6.0)is achieved with 0.40 mg Y(BTC)(H20)6.77.3%of the retained hemoglobin is readily recovered using a 0.5%(m/v)SDS solution as the stripping reagent.Circular dichroism spectra indicated that the conformation of hemoglobin is maintained during the adsorption-desorption process.The MOFs material is applied for the isolation of hemoglobin from human blood and the purity of the obtained hemoglobin is further verified by sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).  相似文献   

16.
Two novel hydrogen maleato (HL) bridged Cu(II) complexes 1[Cu(phen)Cl(HL)2/2] 1 and 1[Cu(phen)(NO3)(HL)2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl2·2H2O and Cu(NO3)2·3H2O, respectively, in CH3OH/H2O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P21/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, Dcalc=1.720 g/cm3 and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, Dcalc=1.734 g/cm3. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χm(T−θ)=0.414 cm3 mol−1 K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively.  相似文献   

17.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = S(CH2)4S, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.  相似文献   

18.
The binuclear molybdenum(II) complexes [Mo2(O2CCF3)4(PR3)2] (R = Ph, Et) act as templates for the self-condensation of 2-aminobenzaldehyde to give a new class of complexes in which a hydride ion bridges two molybdenum(III) centres, each of which carries a tetradentate macrocyclic ligand (C). The new hydrido complexes [Mo2(C)2 (H)(O2CCF3)3(PPh3)2] (I), [Mo2(C)2(H)2(O2CCF3)2(PPh3)2] (II), and [Mo2(C)2 (H)2(O2CCF3)2(PEt3)2]2 (V) exist in two or more isomeric forms as shown by their IR, 1H, 31P and 19F NMR spectra. Substitution with thiocyanate, nitrate and tetraphenylborate anions gives the new products [Mo2(C)2(H)(CO)(NCS)3(PPh3)2] (III), [Mo2(C)2 (H)2(O2CCF3)(NO3)(PPh3)2] (IV), [Mo2(C)2(H)(O2CCF3)(PPh3)2](BPh4)2 (VI) and [Mo2(C)2(H)2(O2CCF3)(PEt3)2](BPh4) (VII), which also exist in isomeric forms.  相似文献   

19.
A potentially decadentate ligand, 1,1,4,7,10,10-hexakis(3,5-dimethyl-1-pyrazolylmethyl)-1,4,7,10-tetraazadecane (tthd), has been synthesized from the reaction of tri-ethylenetetramine with six equivalents of N-hydroxymethyl-3,5-dimethylpyrazole. The tthd ligand forms coordination compounds, M2(tthd)(ClO4)4(H2O)x, when M is Co, Ni, Cu, Zn and Cd and x = 4–8; and M2(tthd)(A)2(ClO4)2(H2O)x when M is Co and Ni, A is NCS or Cl, and x = 4–8. The cobalt compound, Co2(tthd)(ClO4)2(H2O)2(MeOH)1.75, crystallizes in the triclinic space group P1, a = 1.959(2), b = 1.5657(3), c = 2.1244(3) nm, = 105.5(1), β = 96.9(1), γ = 112.1(1). Due to severe disorder of the anions the structure could only be refined to an Rw, value of 0.099. The ligand acts as a decadentate, dinucleating ligand. The cobalt ions are distorted octahedrally surrounded by five N-atoms of the tthd ligand and an O-atom of water occupying the sixth coordination place. The other perchlorate compounds have very similar structures, as can be concluded from spectroscopic data.

In the thiocyanate and chloride compounds the anions have replaced the coordinated water molecules, resulting in octahedral Ni compounds. With Co thiocyanate, however, tthd acts as an octadentate ligand, resulting only in five-coordinated compounds.  相似文献   


20.
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)2X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)2][PF6] (1b: L=CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3.  相似文献   

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