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1.
采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu 2(C 9H 7O 2) 6(C 9H 7O 2H)(C 2H 5OH)]n(1)、[Sm(C 9H 7O 2) 3]n(2)、[Tb(C 9H 7O 2) 3]n(3)和[Gd(C 9H 7O 2) 3]n(4)(C 9H 8O 2=肉桂酸)。 通过X射线单晶衍射确定了它们的结构。 这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。 对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。 分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。 讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。 相似文献
2.
以多齿席夫碱配体H 2L(H 2L=(E)-N′-(3-乙氧基-2-羟基亚苄基)-3-羟基吡啶甲酰肼)为配体,与Ln(acac) 3·2H 2O(Ln=Tb、Ho、Er;acac -=乙酰丙酮根)反应,通过溶剂热法,成功得到了3例新的双核稀土配合物[Ln 2(acac) 2(L) 2(C 2H 5OH) 2](Ln=Tb((1)、Ho((2)、Er(3))。单晶X射线衍射分析表明:配合物1~3的结构主要由2个Ln Ⅲ离子、2个乙酰丙酮根(acac -)、2个L 2-及2个C 2H 5OH组成,中心Ln Ⅲ离子通过2个μ 2-O原子相互连接,形成一个平行四边形的Ln 2O 2核心。固体荧光实验测... 相似文献
3.
合成了一种新的氧化膦取代杯芳烃衍生物的稀土离子(La 3+,Eu 3+)硝酸盐配合物.通过元素分析和红外光谱对配合物进行了表征.在无水甲醇中培养出了配合物的单晶,用X射线单晶衍射法测定了其晶体结构.硝酸镧配合物晶体[L·La(OH 2)(NO 3) 2]NO 3{L为四(亚甲基二苯基氧化膦)杯[4]芳烃}属四方晶系,空间群P4 32 12,晶胞参数a=b=1.8977(4)nm,c=3.1087(11)nm;Z=4;V=11.196(5)nm 3;D c=1.097g/cm 3,F(000)=3712,μ=0.491mm -1,R 1=0.1181,wR 2=0.1930.硝酸铕配合物晶体[L·Eu(OH 2)(NO 3) 2]NO 3·CH 3OH属单斜晶系,空间群C2/c,晶胞参数a=2.88172(11)nm,b=5.4015(2)nm,c=2.01189(7)nm;β=133.4067(9)°,Z=8;V=22.7511(14)nm 3,D c=1.106g/cm 3,F(000)=7464,R 1=0.0671,wR 2=0.1794.2个配合物的晶体结构相类似,配合物中配体的4个磷氧键上的氧原子、2个双齿配位的硝酸根中的4个氧原子还有1个水分子中的氧原子分别参与了配位.中心离子配位数为9,配位多面体为单帽四方反棱柱体.另外在铕配合物的杯芳烃中还包合了1个甲醇分子. 相似文献
4.
合成了配合物Cu(C 14H 9NO 3)(C 3H 4N 2)[C 14H 9NO 32- 为N-(2-羧基苯基)-水杨醛亚胺,C 3H 4N 2为咪唑].晶体属正交晶系,空间群Pca2 1,晶胞参数a=0.94453(12)nm,b=1.12278(9)nm,c=2.9123(4)nm,V=3.0885(6)nm 3,Mr=370.84,Z=8,最终的偏离因子R=0.036,wR=0.087,GOF=0.975.三齿Schiff碱配体中的二个氧原子、一个氮原子和咪唑的一个氮原子与铜原子配位,形成扭曲的平面正方形结构.通过元素分析,IR,UV,CV和TG表征了配合物的结构. 相似文献
5.
合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH 3) 4N] 2[Ni(C 5S 9) 2](1),[(C 2H 5) 4N] 2·[Ni(C 5S 9) 2](2),[(C 4H 9) 4N] 2[Ni(C 5S 9) 2](3),[(C 6H 5)(CH 3) 3N] 2[Ni(C 5S 9) 2](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2. 相似文献
6.
四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在THF溶剂中反应合成了标题配合物Me 4Si 2(C 5H 4) 2LnCl[Ln:3Nd,4Sm,5Gd,6Y]和配合物Me 4Si 2(C 5H 4):Ln(C 5H 5)(THF)n[Ln:1La,n=1;2Pr,n=0].通过元素分析、 1HNMR、13CNMR和MS确证了配合物的结构,在THF溶液中重结晶获得配合物4的单晶,x射线衍射证明晶体结构为二聚体,4为单斜晶系,空间群为P2 1/c,晶体学数据a=1.2982(3)nm,b=1.2269(3)nm,c=1.3681(2)nm,β=96.79(2)°,V=2.162(1)nm 3,Z=2,D x=1.53g/cm 3,偏差因子R=0.068. 相似文献
7.
用Co 2(CO) 8与有机杂环二硫代次膦酸盐SP(C 6H 4OR)(S)N(C 6H 5)NC(Me)(R=Me,Et)反应,得到两类4个含S,P桥基配体的四核钴羰基簇合物Co 4(CO) 10(μ 4-S)[μ 4-P(C 6H 4OR)](1:R=Me;3:R=Et)和Co 4(CO) 10(μ 3-S)[μ 2-P(C 6H 4OR)N(C 6H 5)NC(Me)](2:R=Me,4:R=Et).在反应中,前配体中的PS键以及C-S,P-S,P-N键劈开,产生的分子片与金属钴原子配位,组建成新的羰基钴簇.对这4个簇合物进行了元素分析,IR, 1HNMR和MS谱学表征,并测定了簇合物4的晶体结构,该晶体属单斜晶系,P2 1/c空间群,晶胞参数a=1.9065(4)nm,b=1.0081(2)nm,c=1.6663(3)nm,β=97.36(3)°,V=3.1704(11)nm 3,Z=4,D c=1.743g/cm 3.Co1Co3Co4呈三角形分布,其中Co-Co平均键长为0.251nm,而Co 2在该三角平面的一侧,Co2-Co3键为0.269nm.该簇合物分子骨架为三角钉型结构,每个Co原子的立体几何均为变形八面体,但配位环境各不相同. 相似文献
8.
合成了1,3-丙二胺邻苯二酚钼钨手性八面体配合物(NH 3CH 2CH 2CH 2NH 2) 2[Mo 0.4W 0.6O 2(C 6H 4O 2) 2],并对其进行了单晶结构解析,研究了其与ATP作用的液相NMR谱.该晶体属正交晶系,空间群为Pcan.晶胞参数a=0.7501(2)nm,b=2.3994(7)nm,c=1.2178(4)nm,Z=4.[Mo 0.4W 0.6O 2(C 6H 4O 2) 2] 2-的配位几何构型为手性八面体,晶体为外消旋体.配位阴离子中MoW中心金属离子除了与两个端基O配位形成cis-MO键外,同时还分别与两个邻苯二酚配位基团的的氧原子配位,形成4个M-Ob(M=Mo,W)键,构成两个五元环.利用 1HNMR, 13CNMR, 31PNMR以及 1H- 15NHMBC对标题配合物及其与ATP在D 2O溶剂中的作用进行了研究,发现标题配合物的MoW中心金属离子在纯D 2O溶剂中被还原成+5价,但与ATP混合后转化为+6价,且与原配位基邻苯二酚发生解离.解离后的[MO 2] 2+最大可能与腺嘌呤上的氨基N原子配位,而此配位可能是其抗癌抗肿瘤活性的主要作用机理之一. 相似文献
9.
在水溶液中合成了三乙四胺六乙酸(H 6ttha)钆单核配合物(NH 4) 2[Gd(Httha)]·6H 2O,获得了单晶,并测定了其结构.晶体属单斜晶系,P2 1/c空间群.晶胞参数a=1.0400(4)nm,b=1.2761(4)nm,c=2.3132(4)nm,β=90.89(3)°,V=3.070(2)nm 3,Z=4,D c=1.709g/cm 3.R 1=0.0394,F(000)=1612.配合物是单核分子,每个钆离子与来自同一个三乙四胺六乙酸的4个氮原子和5个羧基氧原子配位,配位数为9,形成单帽四方反棱柱型配位多面体. 相似文献
10.
用Ru 3(CO)12与杂环二硫代次膦酸盐SP(C 6H 4OR)(S)N(C 6H 5)NC(Me)(R=Me,Et)反应,得到两类4个含磷、硫配体的二核和三核钌羰基簇合衍生物Ru 3(CO) 8(μ 3-S) 2[P(C 6H 4OR)N(C 6H 5)NC(Me)S](1;R=Me;3;R=Et)和Ru 2(CO) 6[μ-η 2-SC(Me)NN(C 6H 5)P(C 6H 4OR)](2;R=Me;4;R=Et).对它们进行了元素分析、IR、 1HNMR和MS谱学表征,并用X射线衍射技术测定了1和2的晶体结构.晶体1属三斜晶系,P1空间群,晶胞参数a=1.0755(2)nm,b=1.5760(2)nm,c=0.9078(1)nm,α=98.12(7)°,β=96.64(4)°,γ=79.67(5)°,V=1.4921(4)nm 3,Z=2,R(wR)=0.0303(0.0615);该簇合物分子为开口三核钌簇,其簇骨架Ru 3(μ 3-S) 2为畸变四方锥构型;五元杂环上的P原子取代在Ru1原子的轴向配位位置上.晶体2属单斜晶系,P2(1)/n空间群,晶胞参数a=1.1243(4)nm,b=1.4105(5)nm,c=1.62945(7)nm,β=107.06(5)°,V=2.4702(2)nm 3,Z=4,R(wR)=0.0248(0.0441);两核簇合物分子中含有2个六元螯环Ru1SCNNP和Ru2SCNNP,增强了簇合物的稳定性. 相似文献
11.
采用水热方法合成了4种Sm 3+配合物, 即{[SmZn(2,5-pdc) 2(tp) 0.5(H 2O)]·2H 2O} n(1), [Sm 2Zn 2(C 6H 5COO) 10(Imh) 2(H 2O) 2](2), {[Sm 2(NO 2C 6H 4COO) 6(H 2O) 4]·H 2O} n(3)和{[SmN(CH 2COO) 3(H 2O) 2]·H 2O} n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C 6H 5COO=苯甲酸根, Imh=咪唑, NO 2C 6H 4COO=对硝基苯甲酸根, N(CH 2COO) 3=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm 3+离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm 3+离子发光的敏化作用所致. 此外, 讨论了不同有机配体或 d过渡金属离子对Sm 3+离子发光的影响, 并分析了配合物中Sm 3+离子的近红外发射带位移、 劈裂和加宽的原因. 相似文献
12.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
13.
The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO +, RNC, RN 2+ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH 3OC 6H 4N 2Mo(CO) 2C 5H 5 was prepared by the reaction of NaMo(CO) 3C 5H 5 with p-CH 3OC 6H 4N 2+BF 4−. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN 2M(CO) 2C 5H 5, RN 2M(CO) 2(Pz 3BH) (M = Cr, Mo, W), [(η 6-Me 6C 6)Cr(CO) 2N 2Ar] +, [(MeC 15H 4)M′(CO) 2N 2Ar] + M′ = Mn, Re), [ trans-PhN 2Fe(CO) 2(PPh 3) 2] +, and PhN 2M′(CO) 2(PPh 3) 2(PPh 3) 2 can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH 2N 2M(CO) 2C 5H 5 (R = H or Me 3Si) can be obtained from HM(CO) 3C 5H 5 and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN 2M(CO) 2Q derivatives (Q = C 5H 5, Pz 3BH) include CO substitution reactions, coordination of the second nitrogen in the RN 2 ligand to give heterobimetallic complexes such as C 5H 5Mo(CO) 2(μ-NNC 6H 4Me)(CO) 2C 5H 5, oxidative addition rections with X 2 X = Cl, Br, I), SnX 4, RSSR, and CINO, and reactions with further RN 2+ to give bis(aryldiazenido) derivatives (RN 2) 2MQL + (L = CO, X −, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC 5H 4)M′(CO) 2N 2Ar] + with certain nucleophiles to give (MeC 5H 4)M′(CO) 2N 2. 相似文献
14.
利用(μ 3-CCO 2Et)Co 3(CO) 9与单阴离子试剂[Mo(CO) 3(η 5-C 5H 4R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo 2Mo骨架的簇合物(μ 3-CCO 2Et)Co 2Mo(CO) 8(η 5-C 5H 4R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO) 3[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,W]反应合成了4个双四面体簇合物{(μ 3-CCO 2Et)CoMoM(CO) 7(η 5-C 5H 4R)[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR, 1HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C 2/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm 3,Z=8,D c=1.867g·cm -3,F(000)=2480,R=0.0369,wR=0.1150. 相似文献
15.
The new diphenolato complexes [{Mo(NO){HB(dmpz) 3}Cl} 2Q] where dmpz = 3,5-dimethylpyrazolyl and Q = OC 6H 4(C 6H 4O ( n = 1 or 2), OC 6H 4CR=CRC 6H 4O (R = H or Et), and OC 6H 4CH=CHC 6H 4CH=CHC 6H 4O have been prepared and their electrochemical properties (cyclic and differential pulse voltammetry) compared with previously reported analogues where Q = OC 6H 4O, OC 6H 4EC 6H 4O (E = SO 2, CO and S), OC 6H 4 (CO)C 6H 4 C 6H 4(CO)C 6H 4O and 1,5- and 2,7-O 2C 10H 6. The electrochemical interaction between the redox centres in the new complexes is very weak, in contrast to that in the 1,4-benzenediolato and naphthalendiolato species. The EPR spectra of the reduced mixed-valence species [{Mo(NO){HB(dmpz) 3}Cl} 2Q] − where Q = 1,3- and 1,4-OC 6H 4O and OC 6H 4SC 6H 4O shows that they are valence-trapped at room temperature, whereas those of the dianions [{Mo(NO){HB(dmpz) 3}Cl} 2Q] 2− where Q = 1,4-OC 6H 4O, OC 6H 4EC 6H 4O (E = CO or S) and OC 6H 4CH=CHC 6H 4CH=CHC 6H 4O shows that the unpaired spins on each molybdenum centre are strongly correlated ( J, the spin exchange integral A Mo, the metal-hyperfine coupling constant). The electrochemical properties and the comproportionation constants for the reaction [{Mo(NO){HB(dmpz) 3} Cl} 2Q] + [{Mo(NO){HB(dmpz) 3}Cl}O] 2] 2−2[{Mo(NO) {HB(dmpz) 3}Cl} 2Q] − where Q = diphenolato bridge, are compared with related compounds containing benzenediamido and dianilido bridges. 相似文献
16.
Vogtle等发现,直链醚除具有类似冠醚配位各种金属离子的能力外,还弥补了冠醚的不足之处,如易合成、产率高、价廉等.我们曾报道过有关EPR工作.本文合成了2,4-二羟基苯甲醛缩二甘醇二胺(DHYDA)与镧系的新配合物. 相似文献
17.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
18.
The sterically hindered zinc chalcogenolato complexes [Zn(EAr″) 2] 2 (E = S, Se; Ar″ = 2,4,6-Bu t3C 6H 2) react with 1 equivalent of tert-butylisocyanide in non-coordinating solvents to give Zn(EC 6H 2Bu t3) 2(CNBu t) (1, E = S; 2, E = Se) as thermally stable crystalline adducts; the compounds are thought to be chalcogenolato-bridged dimers. In the presence of excess isocyanide ligand the 1 : 2 adducts Zn(EAr″) 2(CNBu t) 2 (3, E = S; 4, E = Se) are isolated. The compounds represent the first examples of well-characterized isocyanide complexes of zinc. The X-ray structure of 4 showed that it is monomeric with a distorted tetrahedral coordination geometry of the metal centre, which reflects the steric requirements of the chalcogenolato and isocyanide ligands, respectively. 相似文献
19.
报道了配合物Ln(X-P) 3·3H 2O[其中X=H,2-Cl,4-Br,3-OH,3-NO 2,2-OCH 3,2-CH 3,2,4-二氯,P=2-(COO)C 6H 4CONHC 6H 5-nX n,n=1,2;Ln=Pr(Ⅲ),Nd(Ⅲ)]的制备,并用元素分析、红外光谱、电子反射光谱、热重分析进行了表征。结果表明,配位是通过羧酸羟基氧原子和酰胺羰基氧原子进行的,含3分子配位水。通过电子反射光谱数据,对Slater-Condon参量(F k)、Lande参量(ξ 4f)、Nephelauxit比率(β),平均共价参数(δ)、平均成键参数(b 1/2)、F 4/F 2、F 6/F 2比值进行了计算,对配合物的共价成键情况进行了讨论。 相似文献
20.
Substances of the types MH 4ntmp, Mg 3[M(Hntmp)] 2, M 2H 2ntmp and Mg[M 2(Hntmp)] 2, where M = Co, Ni, Cu, Zn and H 6ntmp = N[CH 2PO(OH) 2] 3 were prepared. The sodium and cesium salts of the [Co(Hntmp)] 3− complexes were also prepared. The IR and electronic spectra and the experimental magnetic susceptibilities indicate that these are high-spin complexes. The coordination surroundings of the central atom consist of a highly distorted octahedron of the ligand oxygen atoms. The nitrogen atom is not coordinated to the central atom. 相似文献
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