首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 296 毫秒
1.
铅(II)-氨基多羧酸配合物的合成与结构研究   总被引:1,自引:0,他引:1  
合成了铅(II)与乙二胺四乙酸(EDTA),N-羟乙基乙二胺三乙酸(HEDTA)和 (乙酸-N-羟乙基酯)乙二胺三乙酸(AHEDTA, A = 乙酸-N-羟乙基酯)的配合物,C10H20K2N2O12Pb (K2[Pb(EDTA)]4H2O), C10H22K2N2O11Pb (K2[Pb(HEDTA)]4H2O)和C12H23KN2O11Pb (K[Pb- (AHEDTA)]3H2O), 并测定了K2[Pb(EDTA)]4H2O晶体结构和分子结构。具体测定结果如下:单斜晶系,C2/c空间群,a = 24.59(2),b = 11.79(1),c = 14.08(2) 牛琤 = 108.15(2),V = 3876.0(7)) 3,Z = 8,Mr = 654.65,Dc = 2.213 g/cm3,m = 9.196 mm-1和F(000) = 2480。最终偏差因子分别为R = 0.0458,wR = 0.0640 (对3372 (I > 2.0s(I))可观测衍射点)。在K2[Pb(EDTA)]4H2O中,配合物离子[Pb(EDTA)]2-具有六配位的非标准三棱柱体结构,EDTA作为六齿配体提供4个O原子和2个N原子与中心金属离子Pb2+形成配键。  相似文献   

2.
合成了苯并18-冠-6(B18-C-6)与K_2[Pd(SCN)_4]生成的配合物[K(B18-C-6 )]_(12) [Pd(SCN)_4] (1), [K(B18-C-6)]_2[Pt(SCN)_4] (2)和[K(B18-C-6)]_2 [Pt(SCN)_4]·C_2H_4Cl_2 (3),并通过元素分析、红外光谱、单晶X射线衍射进行 了表征。1和2为单斜晶系,空间群P2_l/n,晶体学数据:1, a = 1.00970(17) nm, b = 1.3157(2) nm, c = 1.7303(3) nm, β = 94.841(2)°, V = 2.2852(7) nm~3, Z = 2, F(000) = 1136, R_1 = 0.0257。3为三斜晶系,空间群P1,晶体学 数据:a = 0.95914(18) nm, b = 1.2137(2) nm, c = 2313(2) nm, α = 63.693 (2)°, β = 76.293(2)°, γ-1.2406(4) n~3, Z = 1 F(000)618,R_1 = 0.0366 。在固态,三个配合物相邻的两个[K(B18-C-6)]~+基团通过冠醚氧化原子与钾的 子的相边接而形成一维链状结构。  相似文献   

3.
合成了二苯并18冠6与Pd,Pt生成的新颖配合物:[K(DB18C6)]2 [Pd(SCN)4] (1), [K(DB18C6)]2 [Pt(SCN)4](2),并通过元素分析、红外光谱、单晶X射线衍射进行了表征.两个配合物均为三斜晶系,空间群P-1.1的晶体学数据:a=0.87375(17)nm,b=1.1900(2)nm,c=1.3180(3)nm,α=73.56(3)°,β=99.90(3)°,γ=82.34(3)°,V=1.298 6(4)nm3,Z=1,F(000)=584,R1=0.075 2,wR2=0.166 0.2的晶体学数据:a=0.855 3(5)nm,b=1.312 7(3)nm,c=1.181 9(3)nm,α=106.21(2)°,β=82.77(3)°,γ=99.72(3)°,V=1.251 6(8)nm3,Z=1,F(000)=818,R1=0.0254,wR2=0.0682.1,2均由两个[K(DB18C6)]+配离子和一个[M(SCN)4]2-配阴离子组成.在固态、配合物两个分子的[K(DB18C6)]+和[M(SCN)4]2-通过K+-π相互作用形成假一维无限链状结构.  相似文献   

4.
我们合成、表征了苯并 1 8 冠 6(B1 8 C 6)与K2 [Pd (SCN) 4 ],K2 [Pt(SCN) 4 ]生成的一维链状配合物 [K(B1 8 C 6) ]2 [Pd(SCN) 4 ]( 1 ) ,[K(B1 8 C 6) ]2 [Pt(SCN) 4 ]( 2 )和[K(B1 8 C 6) ]2 [Pt(SCN) 4 ]·C2 H4Cl2 ( 3 ) .其中 3为三斜晶系 ,空间群P1 [化学学报 2 0 0 2 ,60 ( 8) ,1 465 ].厦门大学胡盛志教授认为该化合物的空间群应为P 1 .经将原始数据重新还原、修正 ,3的空间群的确为P 1 ,现予以更正 .配合物 3部分结构数据由表 1给出 ,其非氢原子坐标和热参数列于表 2 ,部分键长和键角列于表 3 .晶体结构和堆积图…  相似文献   

5.
合成了一种新的烟酸锰配合物,并通过红外光谱﹑热重差热分析﹑元素分析﹑化学分析等手段确定其结构与组成.应用溶解量热法,分别测定了四水氯化锰、烟酸和烟酸锰在常压,298.15 K,混合溶剂(VDMSO∶VEtOH∶V2 mol/L HCl=1∶1∶1)中的溶解焓,△s Hm[MnCl2·4H2O(s),298.15 K]=-(13.596±0.170)kJ·mol-1,△s Hm[2C6H5NO2(s),298.15 K]=(42.780±0.090)kJ·mol-1以及△s Hm[[Mn(C6H4NO2)2]·2H2O,298.15 K]=(15.936±0.070)kJ·mol-1.根据热化学原理求出了反应MnCl2·4H2O(s)+2C6H5NO2(s)=[Mn(C6H4NO2)2]·2H2O(s)+2HCl(g)+2H2O(l).在298.15 K时标准摩尔反应焓△r Hm(1)=(66.42±0.88)kJ·mol-1和配合物[Mn(C6H4NO2)2]·2H2O(s)的标准摩尔生成焓△f Hm[[Mn(C6H4-NO2)2]·2H2O(s),298.15 K]=-(1554.8±2.0)kJ·mol-1.应用TAM air热导式等温微量量热仪测定了烟酸锰配合物[Mn(C6H4NO2)2]·2H2O在301.15 K时对粟酒裂殖酵母细胞生长代谢的产热曲线,计算得到了粟酒裂殖酵母细胞生长速率常数k,最大放热功率时间tp以及总放热量Qtotal等热化学参数.实验结果表明,随着烟酸锰配合物浓度的增加,粟酒裂殖酵母细胞生长代谢速率常数k和总放热量Qtotal减少,即烟酸锰对粟酒裂殖酵母细胞有抑制作用.  相似文献   

6.
By combining trans-4-styrylprydine (tsp) with azide system, we obtained two rare 1D cis-EE-azido-bridged compounds of [M2(N3)4(tsp)4(H2O)2] [M = Mn (1), Co (2)]. The magnetic study reveals that metal ions are anti-ferromagnetically coupled by cis-EE-azido-bridges and they show weak ferromagnetism below 4.0 K (1) and 4.2 K (2) due to the spin-canting caused by asymmetric magnetic interaction.  相似文献   

7.
在278.15~318.15K下, 测定了无液电池(A), Pt, H2│B(OH)3(m1),LiB(OH)4(m)2, LiCl(m3), MgCl2(m4)│AgCl, Ag和电池(B), Pt, H2│B(OH)3(m1), LiB(OH)4(m2), MgCl2(m4)│AgCl, Ag的电动势。利用Debye-Huckel外推法和多项式拟合法确定了硼酸镁离子对[MgB(OH)4^+缔合常数pKt, 并得到了经验方程pKt=A1+A2/T+A3T以及缔合过程的其他各标准热力学量, 同时指出缔合熵是形成[MgB(OH)4^+]离子对的推动力。  相似文献   

8.
合成了两种固态稀土丙氨酸配合物[Ho2(Ala)4(H2O)8]Cl6和[ErY(Ala)4(H2O)8](ClO4)6 (Ala为丙氨酸),用量热和热分析方法研究了这两种配合物的热力学性质.用全自动高精密绝热量热计测定了在78~377 K温区内的低温热容.对于[Ho2(Ala)4(H2O)8]Cl6,在214~255 K温区内发现一固-固相变,其相变温度为235.09 K.对于[ErY(Ala)4(H2O)8](ClO4)6,在99~121 K温区内也发现一固-固相变,其相变温度为115.78 K. [Ho2(Ala)4(H2O)8]Cl6固-固相变焓为3.02 kJ• mol-1,相变熵为12.83 J•K-1•mol-1; [ErY(Ala)4(H2O)8](ClO4)6 固-固相变焓为1.96 kJ•mol-1,相变熵为16.90 J•K-1•mol-1.同时,用TG技术在40~800 ℃温区研究了两配合物的热稳定性.由TG/DTG曲线分析可知, [Ho2(Ala)4(H2O)8]Cl6从80 ℃到479 ℃热分解分两步完成, [ErY(Ala)4(H2O)8](ClO4)6从120 ℃到430 ℃热分解分三步完成.  相似文献   

9.
硼酸盐水溶液热力学研究II: H3BO3-LB(OH)4-LiCl-MgCl2体系   总被引:8,自引:1,他引:8  
宋彭生  王东宝  杨家振 《化学学报》1995,53(10):985-991
在278.15~318.15K下, 测定了无液电池(A), Pt, H2│B(OH)3(m1),LiB(OH)4(m)2, LiCl(m3), MgCl2(m4)│AgCl, Ag和电池(B), Pt, H2│B(OH)3(m1), LiB(OH)4(m2), MgCl2(m4)│AgCl, Ag的电动势。利用Debye-Huckel外推法和多项式拟合法确定了硼酸镁离子对[MgB(OH)4^+缔合常数pKt, 并得到了经验方程pKt=A1+A2/T+A3T以及缔合过程的其他各标准热力学量, 同时指出缔合熵是形成[MgB(OH)4^+]离子对的推动力。  相似文献   

10.
合成了冠醚3,3′-二甲基二苯并-18-冠-6(MDB18-C-6),并以该化合物为配体分别与镍(Ⅱ)、钯(Ⅱ)和K2(i-mnt)作用,进一步合成了配合物[K(MDB18-C-6)(CH3COCH3)]2[Ni(i-mnt)2](1)及配合物[K(MDB18-C-6)(CH3SOCH3)]2[Pd(i-mnt)2](2)。通过元素分析、红外光谱、紫外光谱、核磁共振氢谱、质谱等测试手段对其结构进行表征,用X-射线单晶衍射测定了配合物1和配合物2的晶体结构。利用紫外吸收光谱、荧光光谱和圆二色光谱等光谱分析法研究了配合物与小牛胸腺DNA(CT-DNA)的作用,结果表明两种配合物与DNA都具有相互作用,配合物主要是通过影响DNA的螺旋结构,从而引起DNA的构象变化,并且配合物2的作用性能大于配合物1。  相似文献   

11.
It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…  相似文献   

12.
The crystal structures of [MnTPP]{Ni[S2C2H(CN)]2} [MnTPP = (meso-tetraphenylporphinato)manganese(III)] and [MnTPP]{Ni[S2C2(CN)2]2} have been determined. These salts possess trans-mu-coordination of S = 1/2 {Ni[S2C2H(CN)]2}*- and {Ni[S(2)C(2)(CN)(2)](2)}*- to Mn(III) and form parallel 1-D coordination polymer chains exhibiting nu(CN) at 2210 and 2200 and 2220 and 2212 cm(-1), respectively. The bis(dithiolato) monoanions are planar and bridge two cations with MnN distances of 2.339(16), and 2.394(3) A, respectively, which are comparable to related MnN distances observed for [MnTPP][TCNE].x(solvates). In addition, [MnTP'P]{Ni[S2C2(CN)2]2} {H2TP'P = meso-tetrakis[3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin] and [MnTP'P(OH2)]{Ni[S2C2(CN)2]2} were prepared. The latter forms isolated paramagnetic ions. The room-temperature values of chiT for 1-D [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2} are 2.55, 3.28, and 2.86 emu K/mol, respectively. Susceptibility (chi) measurements between 2 and 300 K reveal weak antiferromagnetic interactions with theta= -5.9 and -0.2 K for [MnTPP]{Ni[S(2)C(2)H(CN)](2)} and [MnTPP]{Ni[S2C2(CN)2]2}, respectively, and stronger antiferromagnetic coupling of -50 K for [MnTP'P]{Ni[S2C2(CN)2]2} from fits of chi(T) to the Curie-Weiss law. The 1-D intrachain coupling, J(intra), of [MnTPP]{Ni[S2C2H(CN)]2} and [MnTPP]{Ni[S2C2(CN)2]2} was determined from modeling chiT(T) by the Seiden expression (H = -2JSi.Sj) with J/kB = -8.00 K (-5.55 cm(-1); -0.65 meV) for [MnTPP]{Ni[S2C2H(CN)]2}, J/kB = -3.00 K (-2.08 cm(-1); -0.25 meV) for [MnTP'P]{Ni[S2C2(CN)2]2}, and J/kB = -122 K (-85 cm(-1)) for [MnTP'P]{Ni[S2C2(CN)2]2}. These observed negative J(intra)/kB values are indicative of antiferromagnetic coupling. These materials order as ferrimagnets at 5.5, 2.3, and 8.0 K, for [MnTPP]{Ni[S2C2H(CN)]2}, [MnTPP]{Ni[S2C2(CN)2]2}, and [MnTP'P]{Ni[S2C2(CN)2]2}, respectively, based upon the temperature at which maximum in the 10 Hz chi'(T) data occurs. [MnTP'P]{Ni[S2C2(CN)2]2} has a coercivity of 17,700 Oe and remanent magnetizations of 7250 emu Oe/mol at 2 K and 17 Oe and 850 emu Oe/mol at 5 K; hence, upon cooling it goes from being a soft magnet to being a very hard magnet.  相似文献   

13.
A new method of synthesizing single-component molecular conductor [Ni(dmit)2] bythe reaction 2(Me4N)[Ni(dmit)2]2→ [Ni(dmit)2] (Me4N)[Ni(dmit)2] is reported. [Ni(dmit)2]exhibits a semiconductive behavior above 167 K, while from 167 K down to the measuring limit of 60 K, it exhibits metallic conductivity.  相似文献   

14.
[{Dy(hfac)(3)}(2){Fe(bpca)(2)}] x CHCl(3) ([Dy(2)Fe]) and [{Dy(hfac)(3)}(2){Ni(bpca)(2)}]CHCl(3) ([Dy(2)Ni]) (in which hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate and bpca(-)=bis(2-pyridylcarbonyl)amine anion) were synthesized and characterized. Single-crystal X-ray diffraction shows that [Dy(2)Fe] and [Dy(2)Ni] are linear trinuclear complexes. Static magnetic susceptibility measurements reveal a weak ferromagnetic exchange interaction between Ni(II) and Dy(III) ions in [Dy(2)Ni], whereas the use of the diamagnetic Fe(II) ion leads to the absence of magnetic exchange interaction in [Dy(2)Fe]. Dynamic susceptibility measurements show a thermally activated behavior with the energy barrier of 9.7 and 4.9 K for the [Dy(2)Fe] and [Dy(2)Ni] complexes, respectively. A surprising negative effect of the ferromagnetic exchange interaction has been found and has been attributed to the structural conformation of these trinuclear complexes.  相似文献   

15.
A new electrical conductive crystal PyEt[Ni(dmit)2]2 (dmit=4,5-dimercapto-1,3-dithiole-2-thione) has been synthesized and its X-ray structure has been determined to be in monoclinic system, C2/c space group. In PyEt[Ni(dmit)2]2 crystal, the conducting component [Ni(dmit)2]0.5- is face-to-face packed forming molecular column along the c-direction, and these molecular columns are then side-by-side extended along the a-direction forming a kind of two-dimensional conducting sheet on (010). The measured conductivity at room temperature along a certain direction on (010) plane is 10 S .cm-1. From 282 to 269 K, the crystal shows metallic behavior but changes to semiconductor below 269 K. Based on the measured crystal structure and calculated band structure, this conductor-semiconductor phase transformation can be primarily interpreted: The metallic conductivity is corresponding to the uniform molecular column and the atomic-lattice-chain structure of Ni chain, while the semi-conductive behavior to staggered mo  相似文献   

16.
Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by two chelating 2,2'-bipy ligands and two cyanides from two different [Ni(CN)4]2- units cis to each other. These compounds have been fully characterized by single-crystal or unconventional powder X-ray diffraction analyses and variable-temperature magnetic measurements.  相似文献   

17.
Doping of spin-ladder systems by isostructural paramagnetic complexes was attempted. Despite the close isostructural nature of the pure (DT-TTF)2[M(mnt)2] (M = Au, Ni, Pt) end-members, which present a ladder structure, doping of the spin-ladder (DT-TTF)2[Au(mnt)2] with either 5% or 25% [M(mnt)2]- (M = Ni, Pt) generates two (metrically) new phases. Their markedly different crystal structures have been determined using laboratory X-ray powder diffraction data. (DT-TTF)2[Au0.75Ni0.25(mnt)2] consists of a mixed-valence compound (of triclinic symmetry), which was only detected, pure or in a mixture of phases, when [Ni(mnt)2]- was used as a dopant. Differently, the stoichiometric 1:1 [DT-TTF][Au0.75Pt0.25(mnt)2] monoclinic phase was found when [Pt(mnt)2]- (in 5% and 25%) was employed as the doping agent. Remarkably, only in the 5% Pt doping experiment, the major component of the mixture was the ladder structure compound (DT-TTF)2[Au(mnt)2] doped with minor amounts of Pt. This 5% Pt-doped specimen shows an EPR signal (g = 2.0115, DeltaHpp = 114 G at 300 K) wider than the pure compound (DT-TTF)2[Au(mnt)2], denoting exchange between the donor spins and Pt(mnt)2- centers. The electrical transport properties of the 5% Pt-doped composition at high temperatures are comparable to those of (DT-TTF)2[Au(mnt)2] with room-temperature conductivity sigma300K = 13 S/cm and thermopower S300K = 46 microV/K, with a sharp transition at 223 K similar to that previously observed in the Cu analogue at 235 K.  相似文献   

18.
One equivalent of [Na2(thf)5-(P4Ph4)] (1) reacts with one equivalent of [Ni(cod)2] (cod=1,5-cyclooctadiene) to give the unexpected ionic compound [Na(Et2O)3][Na3(Et2O)2Ni3(micro-P2Ph2)2-(P2Ph2)3] (2), whereas the reaction of [Ni(cod)2] with the less reactive [K2(pmdeta)2(P4Ph4)] (3) leads to the formation of [K(pmdeta)]2[Ni(P4Ph4)-(P2Ph2)] (4) (PMDETA=NMe(CH2CH2NMe2)2), in which K--Ni interactions are observed. The calculations for 4 confirm the structural parameters obtained by X-ray diffraction studies. A shared electron number (SEN) analysis was applied to investigate the K...Ni interactions. These studies indicate a SEN value of a typical three-center, two-electron bond for K1-Ni-K2 indicating a covalent contribution in the interaction between nickel and potassium.  相似文献   

19.
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-1,10-phenanthroline(NO2-phen) (2), 2,2'-bipyridyl(bpy) (3) and 4,4'-dimethyl-2,2'-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)2.3H2O has been studied in the 4-300 K range, giving the exchange integral J=-109 cm-1. The MT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.  相似文献   

20.
Sandwich-type supramolecular cation structures of (M(+))([12]crown-4)(2) complexes (M(+) = Li(+), Na(+), K(+), and Rb(+)) were introduced as countercations to the [Ni(dmit)(2)](-) anion, which bears an S = (1)/(2) spin, to form novel magnetic crystals (dmit(2-) = 2-thione-1,3-dithiole-4,5-dithiolate). The zigzag arrangement of Li(+)([12]crown-4)(2) cations in Li(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salt induced weak intermolecular interactions of [Ni(dmit)(2)](-) dimers, whose magnetic spins were isolated from each other. The molecular arrangements of cations and anions in M(+)([12]crown-4)(2)[Ni(dmit)(2)](-) salts (M(+) = Na(+), K(+), and Rb(+)) were isostructural to each other. In the case of Na(+)([12]crown-4)(2)[Ni(dmit)(2)](-), the space group C2/m changed to C2/c with a lowering in temperature from 298 to 100 K. This structural change occurred at 222.5 K as a first-order phase transition. The space group C2/m (T = 298 K) in the salt K(+)([12]crown-4)(2)[Ni(dmit)(2)](-) also changed to C2/c (T = 100 K), which transition occurred at 270 K. Crystal structural analyses at 298 and 100 K revealed changes in both supramolecular cation conformation and [Ni(dmit)(2)](-) anion arrangements. The transition from C2/m to C2/c crystals generated a dipole moment in the Na(+)([12]crown-4)(2) and K(+)([12]crown-4)(2) structures, which were reconstructed to cancel the net dipole moment of the C2/c crystals. These cation transformations led to changes in intermolecular interactions between the [Ni(dmit)(2)](-) anions via structural rearrangements. The crystal structure of C2/c was stabilized in Rb(+)([12]crown-4)(2)[Ni(dmit)(2)](-) at 298 K. The [Ni(dmit)(2)](-) configuration in these salts with the C2/c space group was a one-dimensional uniform chain, which showed the temperature-dependent magnetic susceptibility of a one-dimensional linear Heisenberg antiferromagnetic chain.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号