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1.
合成和表征了4种新型配合物[Cu2(TPHA)(NO2-Phen)4](ClO4)2·H2O、[Cu2(TPHA)(Me-bpy)4](ClO4)2、[Mn2(TPHA)(NO2-Phen)4](ClO4)2·2H2O和[Mn2(TPHA)(Me-bpy)4](ClO4)2(TPHA:对苯二甲酸根阴离子;NO2-Phen:5-硝基-1,10-菲绕啉;Me-bpy:4,4'-二甲基-2,2'-联吡…  相似文献   

2.
在不同条件下合成了[Co(phen)mXp]Y1·nH2O型配合物,(m=1,2;p=1,2;1=1-3;n=0-4;phen=邻菲绕啉;X=Cl-,H2O,酒石酸(tart),甘氨酸(gly),α-皮可林酸(pic).DL-两氨酸(ala),L-亮氨酸(leu),L-脯氨酸(pro);Y=Cl-,]并进行了元素分析,热重分析,电子光谱,红外光谱和磁化率测定,计算它们的10Dq和B值.X-ray单晶衍射实验证明:[Co(Phen)2(H2O)2](NO3)3·2H2O,[Co(Phen)2(gly)]Cl2·4H2O均为顺式结构.[Co(Phen)(ala)2]Cl·3H2O,[Co(Phen)(pro)2]ClO4·4/3H2O均为trans(N)结构.在[Co(phen)2X2](n+)型配合物中,X反位的键长均长于顺位键长,其反位效应的顺序为:Cl->羧基,NH2>H2O。  相似文献   

3.
合成了两种稀土高氯酸盐与L-脯氨酸配合物的晶体.经热重、差热、化学分析及对比有关文献,知其组成 是[Pr2(L-Pro)6(H2O)4](ClO4)6和[Er2(L-PrO)6(H2O)4](ClO4)6,质量分数为99.24%和98.20%.选用RE(NO3)· 6H2O(RE=Pr,Er)、LPro、NaClO4·H2O和 NaNO3作辅助物,使用具有恒温环境的反应热量计,以 2 mol·L-1HCl 作溶剂,分别测定了[2RE(NO3)3·6H2O+6L-PrO+6NaClO4·H2O]和{ [RE2(L-PrO)6(H2O)4](ClO4)6+6NaNO3}在 298.15 K时的溶解热.设计一热化学循环求得化学反应的反应焓rH分别是:63.904 kJ·mol-1和 91.017 kJ·mol-1,经计算得配合物[RE2(L-Pro)6(H2O)4](ClO4)6(s)在 298.15 K时的标准生成焓(298.15 K)分别 是-6 594.78 kJ·mol-1和-6 532.87 kJ·mol-1。  相似文献   

4.
合成了3个分别以C2O2-4([Cu2(L1)2(ox)],1),AcO-([Cu2(AcO)(L2)2]BF4,2)和酚氧([Cu2(L3)2](ClO4)2,3)为桥基的双核铜配合物,并测定了1的复配合物[Cu2(L1)2(ox)]·[Fe(OH)2(H2O)4]ClO4·H2O(1′)及2和3的晶体结构.X射线衍射结果表明:1′,2和3分别属于Fddd,P21/c和P21/c空间群.晶胞参数:[Cu2(L1)2(ox)][Fe(OH)2(H2O)4]ClO4·H2O,a=2.4390(4)nm,b=3.0538(6)nm,c=1.8494(6)nm,α=β=γ=90.00°;2,a=0.847(1)nm,b=2.6542(8)nm,c=1.4100(6)nm,β=91.34(6)°;3,a=0.7646(3)nm,b=1.6983(3)nm,c=2.4417(3)nm,β=97.11°  相似文献   

5.
合成了两种以3-硝基邻苯二甲酸根为桥联配体的新型双核钴(Ⅱ)的配合物,即[Co2(3PT)(Phen)4]·(ClO4)2·4H2O(配合物1)和[Co2(3PT)(NPhen)4](ClO4)2·5H2O(配合物2)(3PT=3-硝基邻苯二甲酸根,Phen=1,10-菲口罗啉,NPhen=5-硝基-1,10-菲口罗啉)。使用元素分析,IR,UV-vis和电导测定方法对该两配合物进行了表征。测定了配合物的变温磁化率,并对所得数据进行了理论分析,求得了配合物1、2的磁交换积分均为2J=-9.2cm-1。对配合物进行了体外抗人白血病癌细胞实验。发现该两配合物均具有较强的抑制人白血病癌细胞的活性。  相似文献   

6.
将Gly-GlyO、4,4'-联吡啶与Cu(NO_3)_2·H_2O在二次水溶液中反应,合成出以4,4'-bpy为中继基、Cly-GlyO为螯环的新型双核铜配合物,经X射线单晶结构分析确定该配合物晶体的化学结构式为[(H_2NCH_2CONHCH_2COO)Cu(OH)(C_(10)H_8N_2)Cu(ON)(H_2NCH_2CONHCH_2COO)]·9H_2O.晶体属P 空间群,晶胞参数a=1.1412nm,b=1.2298nm,c=1.4269nm,α=113.82°,β=101.91°,γ=103.64°,Z=2.最终一致性因子R值为0.068,R_w值为0.057,标准偏差σ=0.1951。  相似文献   

7.
合成了3种以4,4'-联吡啶为桥联配体的三核环状Cu(Ⅱ)配合物[Cu_3(4,4'-bpy)_3·(phen)_3](ClO_4)_6·2H_2O(1)、[Cu_3(4,4'-bpy)_3](bpy)_3](ClO_4)_6·H_2O(2)和[Cu_3(4,4'-bpy)_3·(NO_2-phen)_3](ClO_4)_6·6H_2O(3)。经元素分析、电导、IR、电子光谱、ESR、磁化率等方法进行了表征,推定该配合物具有以4,4'-联吡啶为扩展桥的结构。利用Heisenberg模型求得交换参数J值为-0.23cm-1(1)和-0.90cm-1(3),表明配合物中金属离子间仅有很弱的反铁磁交换作用.  相似文献   

8.
本文合成了四个以邻苯二甲酸阴离子为桥联配体的新型希土双核配合物[Ln2(Phth)(NO2-phen)4](ClO4)4·xH2O[Ln=Gd、Tb、Ho、Er,NO2-Phen=5-硝基-1,10-菲咯啉,Phth=邻苯二甲酸阴离子).经元素分析,IR、电导、电子吸收光谱,表征了配合物,测定了[Gd2(Phth)(NO2-phen)4](ClO4)4·4H2O的变温磁化率(4~300K),其数值用最小二乘法与理论方程拟合,求得交换参数J=-2.18cm-1,表明Gd(Ⅲ)-Gd(Ⅲ)离子间存在较弱的反铁磁交换相互作用.  相似文献   

9.
将Gly-GlyO,4,4'-联吡啶与Cu(NO3)2.H2O在二次水溶液中反应,合成出以4,4'-bpy为中继基,Cly-GlyO为螯环的新型双核铜配合物,经X射线单晶结构分析确定该配合物晶体的化学结构式为[(H2NCH2CONHCH2COO)Cu(OH)(C10H8N2)Cu(OH)(H2NCH2CONHCH2COO)].9H2O。晶体属P1空间群,晶胞参数α=1.1412nm,b=1.229  相似文献   

10.
合成和表征了四种新的以二硫代草酰胺基(dtO2-)或二环己酮草酰二腙(BCO)作桥基的双核金属配合物[Cu2(phen)2(dtO)](ClO4)2(1)、[Cu2(dien)2(dtO)](ClO4)2·2H2O(2)、[Ni2(dien)2(H2O)2(dtO)](ClO4)2(3)及[Cu2(phen)2(ClO4)2(BCO)](ClO4)2(4),(phen:1,10-邻菲咯啉,dien:二乙烯三胺)。测定了配合物1和4的变温磁化率,并求出交换积分J分别为-7.67(1)和-0.92(4)cm-1,表明双核配合物中铜离子间存在反铁磁性自旋交换相互作用。  相似文献   

11.
本文用改进和半微量相平衡方法研究了Y(ClO~4)~3.3H~2O-18C~6-CH~3Cn 三体系在20℃时的溶解度, 以便确定三水高氯酸钇与18-冠-6-在乙腈中能否形成配合物, 能生成几种配合物以及它们的相区情况, 为合成固态配合物提供依据。并在该基础上, 分离,制备了固态配合物, 利用化学分析, DTG,TG,DSC以及电导考查了配合物的组成与性质。  相似文献   

12.
在溶液中,室温下对含有穴醚N8O3配体(H3L)的金属大环化合物[Na(H3L)](ClO4)3H2O(2)和[La(H3L)(OH)2](ClO4)3(3),作了1HNMR谱的测定,在化合物(2)-乙腈溶液中加入过量La(ClO4)3后的(2+La)和化合物(3)还作了13C和1H-1HCOSY(氢-氢相关二维谱)、1H-13CHMQC(氢核检测的异核多量子相干相关谱)及1H-13CHMBC(氢核检测的异核多键相关谱)的NMR谱测定,归属了所有1H,13C的谱线。对其配位行为通过1HNMR试验作了简单的讨论。  相似文献   

13.
稀土与不同端基直链聚醚配合物的合成及其NMR研究   总被引:1,自引:0,他引:1  
合成了稀土高氯酸盐分别与一缩二乙二醇二甲醚(EO_2Me_2)和一缩二乙二醇-二-(邻甲氧基苯基)醚[EO_2(MeOP)_2]形成的两系列17种新的配合物,经元素分析、IR、NMR表征,确定配合物组成为Ln_3(ClO_4)_9(EO_2Me_2)_5·18H_2O(Ln=La,Pr,Nd)和Ln(ClO_4)_3EO_2Me_2·8H_2O(Ln=Sm,Eu,Gd,Tb,Dy,Ho,Er,Yb,Y)及Ln(ClO_4)_3EO_2(MeOP)_2·6H_2O(Ln=La,Pr,Nd,Eu,Gd).讨论了它们的NMR及光谱等性质,研究了不同端基直链聚醚对配位作用的影响。  相似文献   

14.
The versatility of the carbonato complex [Co(trpn)CO3]ClO4·H2O as a good source for the preparation of a series of octahedral cis-cobalt(III)-trpn complexes was demonstrated. The compound was used to synthesize complexes of the type [Co(trpn)XY]ClO4, where XY= (NO2)2, (OCN)2, (SCN)2, (N3)2, (OH)2, (SCN)(NO2), C6H5O·PO3, p-NO2C6H4OPO3 and DPA. A second series of complexes formulated as [Co(trpn)L](ClO4)2 were prepared where L=phCO2, p-NO2C6H4CO2, pic and amino acid anions of glycine, l-leucine, and l-norvaline, as well as [Co(trpn)(dl-Hpha)](ClO4)3·4H2O (Hpha=phenylalanine). The isolated complexes were characterized by elemental analyses, i.r. and u.v.–vis. spectra. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

15.
Treatment of a dinuclear zinc hydroxide complex ([(bmnpaZn)(2)(mu-OH)(2)](ClO(4))(2) (1) or [(benpaZn)(2)(mu-OH)(2)](ClO(4))(2) (2)) with excess equivalents of an aryl alcohol derivative (p-HOC(6)H(4)X; X = NO(2), CHO, CN, COCH(3), Br, H, OCH(3)) yielded the nitrogen/sulfur-ligated zinc aryloxide complexes [(bmnpa)Zn(p-OC(6)H(4)NO(2))](ClO(4)) (3), [(benpa)Zn(p-OC(6)H(4)NO(2))](ClO(4)) (4), [(benpa)Zn(p-OC(6)H(4)CHO)](ClO(4)) (5), [(benpa)Zn(p-OC(6)H(4)CN)](ClO(4)) (6), [(benpa)Zn(p-OC(6)H(4)COCH(3))](ClO(4)) x 0.5H(2)O (7), [(benpa)Zn(p-OC(6)H(4)Br)](ClO(4)) (8), [(benpa)Zn(p-OC(6)H(5))](ClO(4)) (9), and [(benpa)Zn(p-OC(6)H(5)OCH(3))](ClO(4)) (10). The solid state structures of 2, 3, 5, and 6 have been determined by X-ray crystallography. While 3 and 6 exhibit a mononuclear zinc ion possessing a distorted five-coordinate trigonal bipyramidal geometry, in 5 each zinc center exhibits a distorted six-coordinate octahedral geometry resulting from coordination of the aldehyde carbonyl oxygen of another zinc-bound aryloxide ligand, yielding a chain-type structure. Zinc coordination of the aldehyde carbonyl of 5 is indicated by a large shift (>40 cm(-)(1)) to lower energy of the carbonyl stretching vibration (nu(C[double bond]O) in solid state FTIR spectra of the complex. In the solid state structures of 3, 5, and 6, a hydrogen-bonding interaction is found between N(3)-H of the supporting bmnpa/benpa ligand and the zinc-bound oxygen atom of the aryloxide ligand (N(3)...O(1) approximately 2.78 A). Solution (1)H and (13)C NMR spectra of 3-10 in CD(3)CN and FTIR spectra in CH(3)CN are consistent with all of the aryloxide complexes having a similar solution structure, with retention of the hydrogen-bonding interaction involving N(3)-H and the oxygen atom of the zinc-coordinated aryloxide ligand. For this family of zinc aryloxide complexes, a correlation was discovered between the chemical shift position of the N(3)-H proton resonance and the pK(a) of the parent aryl alcohol. This correlation indicates that the strength of the hydrogen-bonding interaction involving the zinc-bound aryloxide oxygen is increasing as the aryloxide moiety increases in basicity.  相似文献   

16.
The present work carried out a study on perchlorate mixed-ligand copper(II) complexes which have been synthesized from ethylenediamine derivatives (3a-c) and beta-diketones. These complexes, namely [Cu(DA-Cl)(acac)H(2)O]ClO(4)4, [Cu(DA-Cl)(bzac)H(2)O]H(2)O.ClO(4)5, [Cu(DA-OMe)(acac)H(2)O]ClO(4)6, [Cu(DA-OMe)(bzac)H(2)O]ClO(4)7, [Cu(DA-H)(acac)H(2)O]2H(2)O.ClO(4)8 and [Cu(DA-H)(bzac)H(2)O]ClO(4)9 (where acac, acetylacetonate and bzac, benzoylacetonate) were characterized by elemental analysis, spectral (IR and UV-vis) and magnetic moment measurements. Thermal properties and decomposition kinetics of all complexes are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters (E, A, DeltaH, DeltaS and DeltaG) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. The biochemical studies showed that, the diamines 3a-c have powerful effects on degradation of DNA and protein. The antibacterial screening demonstrated that, the diamine (DA-Cl), 3b has the maximum and broad activities against Gram +ve and Gram -ve bacterial strains.  相似文献   

17.
Five new trinuclear Cu-Ln-Cu cluster complexes have been prepared by a one-pot reaction using H3bcn (tris- N,N',N'-(2-hydroxybenzyl)-1,4,7-triazacyclononane) and Ln = La(III), Nd(III), Gd(III), Dy(III), and Yb(III) where the d- and f-block metal ions are in close proximity desirable for magnetic studies. The [LnCu2(bcn)2]ClO4.nH2O complexes possess the same stoichiometry as the previously reported [LnNi2(bcn)2]ClO4.nH2O and [LnZn2(bcn)2]ClO4.nH2O systems. Additionally, the solid state structures of the LnCu2 complexes appear to be isostructural to the LnNi2 and LnZn2 species as determined by their nearly superimposable IR spectra. The similarities in the structures of the [LnTM2(bcn)2]ClO4.nH2O series, where TM = Zn(II), Ni(II), and Cu(II), allow for direct comparison of their magnetic exchange. An empirical approach, removing first-order anisotropic contributions determined from the analogous [LnZn2(bcn)2]ClO4.nH2O was used to study the d/f/d spin interactions in the [LnCu2(bcn)2]ClO4.nH2O complexes. A ferromagnetic exchange was determined where Ln = Gd(III), Dy(III), or Yb(III) and an antiferromagnetic exchange for Ln = Nd(III), identical to the magnetic exchange observed for the [LnNi2(bcn)2]ClO4.nH2O complexes. An exchange integral of 3.67 cm(-1) for the trimetallic [GdCu2(bcn)2]ClO4.3H2O species was determined using a modified spin Hamiltonian. The [Cu(Hbcn)] and the [Cu3(Hbcn)2](ClO4)2 building blocks of the larger coaggregated d/f/d species were also synthesized, and their structures are reported.  相似文献   

18.
Cobalt(II) complexes of reduced glutathione (GSH) of general composition Na[Co(L)(X)].nH2O (where H2L = GSH; X = Cl-, NO3-, NCS-, CH3CO2-, HCO2-, ClO4- and n = 0-4) have been synthesized and characterised by elemental analyses, vibrational spectra, electronic spectra, magnetic susceptibility measurements, thermal studies and molecular modeling studies. Electronic spectra indicate planar geometry for all the complexes. Infrared spectra indicate the presence of H2O molecules (except perchlorate complex) in the complexes that has been supported by TG/DTA. The room temperature magnetic moment values for all complexes lie in the range of 2.60-2.80 BM range indicating departure from spin only values due to second order Zeeman effect. Thermal decomposition of all the complexes proceeds via first order kinetics. The Na[Co(L)(Cl)].2H2O complex has the minimum activation energy and Na[Co(L)(CH3CO2)].3H2O has the maximum activation energy. The molecular modeling calculation for energy minimization optimizes geometry of the metal complexes.  相似文献   

19.
Three new dinuclear complexes, [(tmen) (H2O)2Ni (Hdmg)(dmg)Cu]·ClO4, [(dien)(H2O)Ni (Hdmg)(dmg) Cu]·ClO4 and [(tmen)Cu(Hdmg)(dmg) Cu] ClO4·H2O (H2dmg=dimethylglyoxime, tmen=tetramethylene diamine), have been prepared. Variable-temperature- magnetic susceptibility measurements (75–300K) on the complexes reveal the presence of intramolecular antiferromagnetic interactions through the oximate bridges. The formation of mononuclear, dinuclear complexes has been confirmed by spectrophotometry.  相似文献   

20.
The new five macrocyclic ligands were synthesized by reaction of 2,6-diaminopyridine and various dialdehydes. Then, their copper(II) perchlorate complexes were synthesized by template effect by reaction of 2,6-diaminopyridine, Cu(ClO(4))(2).6H(2)O and aldehydes. The ligands and their complexes have been characterized by elemental analysis, IR, (1)H and (13)C NMR, UV-vis spectra, magnetic susceptibility, conductivity measurements, mass spectra. All complexes are diamagnetic and binuclear. The diamagnetic behaviour of the binuclear complexes may be explained by a very strong anti-ferromagnetic interaction in the Cu-Cu pair.  相似文献   

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