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1.
本文报道了四种新的双核钴(Ⅱ)配合物,即[Co2(4Br-TPHA)(L)4](ClO4)(4Bk-TPHA=四溴代对苯二甲酸根阴离子,L=1,10-菲咯啉(phen)(1),5-硝基-1,10-菲咯啉(NO2-phen)(2),2,2'-联吡啶(bpy)(3)和4,4'-二甲基-2,2'-联吡啶(Me2bpy)(4))的合成的表征,基于IR光谱、元素分析、电导测量等方法推定配合物具有四溴代对苯二  相似文献   

2.
本文合成了两个新的双核配合物,[Cu(sampn)Ni(L)_2],sampn~(4-)表示N,N′-1,2-丙二水杨酰胺根阴离子,L表示2,2-联吡啶(bpy)或1,10-菲咯啉(phen),经元素分析,IR和电子光谱等方法已推定配合物具有酚氧桥结构和Cu(Ⅱ)及Ni(Ⅱ)的配位环境分别为平面四方及八面体构型,配合物的变温磁化率已测(4—300K),其数值用最小二乘法和从自旋哈密顿算符 =-2J _1 _2导出的磁方程拟合,求得交换参数为J=-1.90cm~(-1)(bpy)和J=-1.68cm~(-1)(phen),表明两个Cu(Ⅱ)-Ni(Ⅱ)双核配合物中有弱的反铁磁自旋交换相互作用。  相似文献   

3.
文报道了四种新的双核钴(Ⅱ)配合物,即[Co2(4Br-TPHA)(L)4](ClO4)(4Br-TPHA=四溴代对苯二甲酸根阴离子,L=1,10-菲咯啉(phen)(1),5-硝基-1,10-菲咯啉(NO2-phen)(2),2,2′-联吡啶(bpy)(3)和4,4′-二甲基-2,2′-联吡啶(Me2bpy)(4))的合成和表征,基于IR光谱、元素分析、电导测量等方法推定配合物具有四溴代对苯二甲酸根桥联结构和Co(Ⅱ)离子具有畸变的八面体配位环境,配合物的变温磁化率(75-300K)已测,其数据已用从自旋哈密顿算符H=-2JS1·S2导出的磁方程拟合,求得交换参数为J=-0.88cm-1(1),J=-0.86cm-1(2),J=-0.89cm-1(3),J=-0.90cm-1(4),表明金属离子间有弱的反铁磁性自旋变换相互作用。  相似文献   

4.
合成和表征了四种新的异三核配合物, {[Mn(L)2]2[Cu(bpa)]{(ClO4)2,其中pba表示为亚丙基-1, 3-双(草胺酸根); L表示1, 10-菲咯啉(phen)、5-硝基-1, 10-菲咯啉(NO2-phen)、2, 2'-联吡啶(bpy)、4, 4'-二甲基-2, 2'-联吡啶(Me2bpy)。基于{[Mn(phen)2]2[Cu(pba)]}(ClO4)2.H2O的变温磁化率测量(4.2~300K), 求出交换积分J=41.5cm^-^1, 表明Mn(Ⅱ)和Cu(Ⅱ)离子间为反铁磁耦合。在XMT-T图上, XMT在175K附近呈现出一极小值, 这是具有非正规自旋态结构的多金属耦合体系的典型特征。  相似文献   

5.
邓洪  李红  徐宏  计亮年 《化学学报》2002,60(12):2159-2166
合成了4-氰基苯基咪唑并[5,6-f]邻菲咯啉(CYIP)和2-羧基苯基咪唑并[5, 6-f]邻菲咯啉(COIP)两种新配体及它们的钌混配配合物[Ru(bpy)2CYIP](ClO4)2 ·H2O(Rul)(bpy=2,2′-联吡啶),[Ru(phen)2CYIP](ClO4)2·H2O(Ru2) (phen=1,10-邻菲咯啉),[Ru(bpy)2COIP](ClO4)2·3H2O(Ru3)和[Ru(phen)2COIP] (ClO4)2·H2O(Ru4),并用红外光谱、紫外光谱、核磁和质谱对它们进行了表征。 通过循环伏安法研究了这些配合物的电化学性质。采用电子吸收光谱、稳态荧光、 圆二色谱和粘度测定研究了配合物与小牛胸腺DNA的相互作用。结果表明配合物 Rul和Ru2通过CYIP配体以插入的方式与DNA结合,而配合物Ru3和Ru4则通过COIP配 体以部分插入的方式与DNA结合。  相似文献   

6.
合成和表征了4种以四溴代邻苯二甲酸根阴离子(4Br-PHTH)桥联、以1,10-菲咯啉(phen),5-硝基-1,10-菲咯啉(NO_2-phen),2,2′-联吡啶(bpy)和4,4′-二甲基-2,2′-联吡啶(Me_2bpy)端接的双核钴(Ⅱ)配合物[Co_2(4Br-PHTH)(L)_4](ClO_4)(L=phen(l),NO_2-phen(2),bpy(3),Me_2bpy(4))。基于IR光谱、元素分析、电导测量等方法推定配合物具有四溴代邻苯二甲酸根桥联结构和Co(Ⅱ)离子具有畸变的八面体配位环境。进行了配合物变温磁化率(75~300K)的测定,其数据已用从自旋哈密顿符导出的磁方程拟合,求得交换参数J=-0.87cm~(-1)(1),-0.84cm~(-1)(2),-0.82cm~(-1)(3),-0.85cm~(-1)(4),表明金属离子间有弱的反铁磁性自旋交换相互作用。  相似文献   

7.
合成和表征了四种新的异三核配合物,{[Mn(L)_2]_2[Cu(Pba)]}(ClO_4)_2,其中Pba表示为亚丙基-1,3-双(草胺酸根);L表示1,10-菲咯啉(phen)、5-硝基-1,10-菲咯琳(NO_2-phen)、2,2’-联吡啶(bpy)、4,4′-二甲基-2,2’-联吡啶(Me_2bpy).基于{[Mn(phen)_2]_2[Cu(pba)]}(ClO_4)_2·H_2O的变温磁化率测量(4.2~300K),求出交换积分J=-41.5cm(-1),表明Mn(Ⅱ)和Cu(Ⅱ)离子间为反铁磁耦合.在 X_MT-T图上,X_MT在175K附近呈现出一极小值,这是具有非正规自旋态结构的多金属耦合体系的典型特征.  相似文献   

8.
合成和表征了四个新的大环上含有草酰胺桥基的双核配合物[Cu(η-L1)ML22](ClO4)2·nH2O,其中L1为2 ,3 -二羰基-5 ,6 : 13, 14-二苯基-1 ,4 ,8 , 11-四氮杂十四环-7 , 11-二烯;L2 =乙二胺(en),M=Cu(1),M=Ni(2);L2 = 1 ,10-邻菲咯啉(phen),M=Cu(3),M=Ni(4)。测定了配合物(3)和(4)的变温磁化率(4 .2 -300K),求得磁参数分别为(3)J=-99.1 cm-1 和(4)J=-47.0 cm-1,表明Cu(Ⅱ)、-Cu(Ⅱ)、Cu(Ⅱ)-Ni(Ⅱ)离子间存在反铁磁自旋交换相互作用。  相似文献   

9.
手性双核钌(Ⅱ)配合物与DNA的相互作用研究   总被引:1,自引:0,他引:1  
本文合成了1对手性双核钌(Ⅱ)配合物ΔΔ-和ΛΛ-[(bpy)2Ru(mbpibH2)Ru(bpy)2](ClO4)4(bpy=2,2′-联吡啶,mbpibH2=1,3-二(咪唑并[4,5-f][1,10-邻菲咯啉])苯)。通过元素分析、质谱、核磁共振、CD光谱对这两个化合物进行了结构表征。采用循环伏安法对配合物的电化学性质进行了分析。利用紫外-可见吸收光谱滴定、荧光光谱滴定  相似文献   

10.
本文通过溶剂热方法合成了四个新的混合配体配合物[Zn(dba)(bpy)]n(1),{[Zn(dba)(phen)]·2H20}。(2),[Cd(dba)(bpy)(H20)2](3)和[Cd2(dba)2(phen)2]n(4)(H2dba=2,5-二羟基对苯二乙酸,bpy=2,2'-联吡啶,phen=1,10。菲咯啉).对这四个化合物进行了单晶衍射、红外光谱、元素分析和粉末X-射线衍射等表征.化合物1和2具有1D无限链状结构,化合物3为单核构型,化合物4是由H2dba配体桥联的双核对称单元组装成的2D网络结构.对这几个化合物的荧光性质进行了研究.  相似文献   

11.
The reactions of bidentate diimine ligands (L2) with binuclear [Ru(L1)(CO)Cl2]2 complexes [L1 not equal to L2 = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), di(2-pyridyl)ketone (dpk), di(2-pyridyl)amine (dpa)] result in cleavage of the dichloride bridge and the formation of cationic [Ru(L1)(L2)(CO)Cl]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(phen)(CO)Cl]+, [Ru(4,4'-Me2bpy)(5,6-Me2phen)(CO)Cl]+ (as two polymorphs), [Ru(4,4'-Me2bpy)(4,7-Me2phen)(CO)Cl]+, [Ru(bpy)(dpa)(CO)Cl]+, [Ru(5,5'-Me2bpy)(dpa)(CO)Cl]+, [Ru(bpy)(dpk)(CO)Cl]+, and [Ru(4,4'-Me2bpy)(dpk)(CO)Cl]+ cations were confirmed by single crystal X-ray diffraction studies. In each case, the structurally characterized complex had the carbonyl ligand trans to a nitrogen from the incoming diimine ligand, these complexes corresponding to the main isomers isolated from the reaction mixtures. The synthesis of [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)(NO3)]+ from [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)Cl]+ and AgNO3 demonstrates that exchange of the chloro ligand can be achieved.  相似文献   

12.
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-l,10-phenanthroline(NO2-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)23H2O has been studied in the 4–300 K range, giving the exchange integral J—109 cm?1. The HMT 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   

13.
Reactions between the Os(VI)-nitrido complexes, [OsVI(L2)(Cl)3(N)] (L2 = 2,2'-bipyridine (bpy) ([1]), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and 4,7-diphenyl-1,10-phenanthroline (Ph2phen)), and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) in dry CH3CN at 60 degrees C under N2 give the corresponding Os(IV)-azidoimido complexes, [OsIV(L2)(Cl)3(NN3)]- (L2 = bpy = [2]-, L2 = Me2bpy = [3]-, L2 = phen = [4]-, and L2 = Ph2phen = [5]-) as their PPN+ salts. The formulation of the N42- ligand has been substantiated by 15N-labeling, IR, and 15N NMR measurements. Hydroxylation of [2]- at Nalpha with O<--NMe3.3H2O occurs to give the Os(IV)-azidohydroxoamido complex, [OsIV(bpy)(Cl)3(N(OH)N3)] ([6]), which, when deprotonated, undergoes dinitrogen elimination to give the Os(II)-dinitrogen oxide complex, [OsII(bpy)(Cl)3(N2O)]- ([7]-). They are the first well-characterized examples of each kind of complex for Os.  相似文献   

14.
Treatment of [RhCl(eta4-diene)]2 (diene = nbd, cod) with the N-heterocyclic ligands 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and pyridine (py) followed by addition of Cs[arachno-6-SB9H12] affords the corresponding salts, [Rh(eta4-diene)(L2)][SB9H12] [diene = cod, L2 = bpy (1), Me2bpy (3), phen (5), (py)2 (7); diene = nbd, L2 = bpy (2), Me2bpy (4), phen (6), (py)2 (8)]. These compounds are characterized by NMR spectroscopy and mass spectrometry, and in addition, the cod-Rh species 1 and 3 are studied by X-ray diffraction analysis. These saltlike reagents are stable in the solid state, but in solution the rhodium(I) cations, [Rh(eta4-diene)(L2)]+, react with the polyhedral anion [SB9H12]- leading to a chemistry that is controlled by the d8 transition element chelates. The nbd-Rh(I) complexes react faster than the cod-Rh(I) counterparts, leading, depending on the conditions, to the synthesis of new rhodathiaboranes of general formulas [8,8-(L2)-nido-8,7-RhSB9H10] [L2 = bpy (9), Me2bpy (10), phen (11), (py)2 (12)] and [8,8-(L2)-8-(L')-nido-8,7-RhSB9H10] [L' = PPh3, L2 = bpy (13), Me2bpy (14), phen (15); L' = NCCH3, L2 = bpy (16), Me2bpy (17), phen (18)]. Compound 13 is characterized by X-ray diffraction analysis confirming the 11-vertex nido-structure of the rhodathiaborane analogues 14-18. In dichloromethane, 1 and 3 yield mixtures that contain the 11-vertex rhodathiaboranes 9 and 10 together with new species. In contrast, the cod-Rh(I) reagent 5 affords a single compound, which is proposed to be an organometallic rhodium complex bound exo-polyhedrally to the thiaborane cage. In the presence of H2(g) and stoichiometric amounts of PPh3, the cod-Rh(I) reagents, 1, 3, and 5, afford the salts [Rh(H)2(L2)(PPh3)2][SB9H12] [L2 = bpy (19), Me2bpy (20), phen (21)]. Similarly, in an atmosphere of CO(g) and in the presence of PPh3, compounds 1-6 afford [Rh(L2)(PPh3)2(CO)][SB9H12] (L2 = bpy (22), Me2bpy (23), phen (24)]. The structures of 19 and 24 are studied by X-ray diffraction analysis. The five-coordinate complexes [Rh(L2)(PPh3)2(CO)]+ undergo PPh3 exchange in a process that is characterized as dissociative. The observed differences in the reactivity of the nbd-Rh(I) salts versus the cod-Rh(I) analogues are rationalized on the basis of the higher kinetic lability of the nbd ligand and its faster hydrogenation relative to the cod diene.  相似文献   

15.
The hydrothermal reaction of Cd(II) salt with 5-[(2-methyl-1H-imidazol-1-yl)methyl]isophthalic acid (H2L) leads to the formation of a new complex [Cd(L)(H2O)] (1). While in the presence of 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) as auxiliary ligands, complexes [Cd(L)(bpy)]?H2O (2) and [Cd(L)(phen)]?2H2O (3) were obtained. Complexes 1–3 have been characterized by single crystal and powder X-ray diffractions, IR, and elemental and thermogravimetric analyzes. As a result, complex 1 exhibits twofold interpenetrated 3-D (10,3)-a architecture, 2 displays chain structure, and 3 shows uninodal 3-connected hcb network with (63) topology. The impact of auxiliary ligands on the structures of resultant complexes is discussed. Moreover, luminescence property of 1–3 was investigated.  相似文献   

16.
Four tripodal sensitizers, Ru(bpy)(2)(Ad-tripod-phen)(2+) (1), Ru(bpy)(2)(Ad-tripod-bpy)(2+) (2), Ru(bpy)(2)(C-tripod-phen)(2+) (3), and Ru(bpy)(2)(C-tripod-bpy)(2+) (4) (where bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and Ad-tripod-bpy (phen) and C-tripod-bpy (phen) are tripod-shaped bpy (phen) ligands based on 1,3,5,7-tetraphenyladamantane and tetraphenylmethane, respectively), have been synthesized and characterized. The tripodal sensitizers consist of a rigid-rod arm linked to a Ru(II)-polypyridine complex at one end and three COOR groups on the other end that bind to metal oxide nanoparticle surfaces. The excited-state and redox properties of solvated and surface-bound 1-4 have been studied at room temperature. The absorption spectra, emission spectra, and electrochemical properties of 1-4 in acetonitrile solution are preserved when 1-4 are bound to nanocrystalline (anatase) TiO(2) or colloidal ZrO(2) mesoporous films. This behavior is indicative of weak electronic coupling between TiO(2) and the sensitizer. The kinetics for excited-state decay are exponential for 1-4 in solution and are nonexponential when 1-4 are bound to ZrO(2) or TiO(2). Efficient and rapid (k(cs) > 10(8) s(-)(1)) excited-state electron injection is observed for 1-4/TiO(2). The recombination of the injected electron with the oxidized Ru(III) center is well described by a second-order kinetic model with rate constants that are independent of the sensitizer. The sensitizers bound to TiO(2) were reversibly oxidized electrochemically with an apparent diffusion coefficient approximately 1 x 10(-11) cm(2) s(-)(1).  相似文献   

17.
Four binuclear Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) complexes bridged by oxamidate (oxd) group have been synthesized, namely Co2(byp)2(oxd)(ClO4)2 (1), Co2(Me2bpy)2(oxd)(ClO4)2.H2O (2), Ni2(bpy)2(oxd)(ClO4)2.2H2O (3) and Cu2(Me2bpy)2(oxd)(NO3)2 (4). (bpy=2,2'-bipyridyl, Me2-bpy=4,4'-dimethylbipyridyl, oxd=oxamidate) The complexes are characterized by IR, UV spectra, EPR and variable-temperature magnetic susceptibility (4-300 K). The susceptibility data for. complexes 1 and 3 were least-squares fit to the susceptibility equation derived from the spin Hamiltonian H=-2J . S1 . S2. The exchange integral, J, was found to be equal to -3.62 cm-1 in 1 and -1.82 cm-1 in 3. This indicates a weak antiferromagnetic spin exchange interaction between the metal ions.  相似文献   

18.
Six new μ-phthalato binuclear oxovanadium(IV) complexes, namely [(VO)2(PHTH)-(L)2]SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2 bpy); 5-nitro-1,10-phenanthroline (NO2-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-1,10-phenanthroline (CH3-phen), where PHTH is the phthalate dianion), have been synthesized and characterized by elemental analyses, IR, electronic spectra, magnetic moments at room temperature and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complexes [(VO)2(PHTH)(phen)2]SO4 (1) and [(VO)2(PHTH)(CH3-phen)2]SO4 (2) was measured in 4—300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, ?=?2J?1·?2, giving the exchange integrals J=?12.8 cm?1 for 1 and J=?7.9 cm?l for 2. This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.  相似文献   

19.

This paper reports the synthesis, crystal structure and properties of two new mononuclear nickel(II) complexes, [NiL(phen)][ClO4]2(1) and [NiL(bpy)][ClO4]2(2), where L is bis(benzimidazol-2-ylmetheyl)(2-hydroxyethyl)amine and phen and bpy are 1,10-phenanthroline and 2,2'-bipyridine, respectively. The crystal structure of 1 ·2EtOH has been determined by single-crystal X-ray analysis. It crystallizes in the monoclinic system, space group C2/c, a= 24.279(2), b= 20.864(2), c= 17.635(1)Å, g = 121.730(2)°, Z= 8, R 1= 0.064, wR 2= 0.167. The Ni(II) ion in 1 ·2EtOH is coordinated to three nitrogen atoms and one oxygen atom of the ligand L and two nitrogen atoms of phen to form a distorted octahedron. Spectroscopic properties of 1 and 2 are reported.  相似文献   

20.
Four succinato-bridged complexes of copper(II) have been synthesized. Complex 1, [Cu(2)(mu-OH(2))(2)L(bpy)(2)(NO(3))(2)](n) and 2, [Cu(2)(mu-OH(2))(2)L(phen)(2)(NO(3))(2)](n)(bpy = 2,2[prime or minute]-bipyridine; phen = 1,10-phenanthroline and LH(2)= succinic acid) exhibit 1D coordination polymer structures where both the nitrate ions are directly linked to the copper(ii) producing synthons in a 2D sheet. A novel 2D grid-like network, ([Cu(4)L(2)(bpy)(4)(H(2)O)(2)](ClO(4))(4)(H(2)O))n3, is obtained upon changing the nitrate by perchlorate anion in complex 1, where the channels are occupied by the anions. On changing the nitrate by tetrafluoroborate anion in complex 2, a novel octanuclear complex, [Cu(8)L(4)(phen)(12)](BF(4))(8).8H(2)O 4, is isolated. The coligand bpy and phen in these complexes show face-to-face (in 1,2,3,4) or edge-to-face (in 4 )pi-pi interactions forming the multidimensional supramolecular architectures. Interestingly, the appearance of edge-to-face pi-pi interactions in complex facilitates the formation of discrete octanuclear entities. Variable-temperature (300-2 K) magnetic measurements of complexes have been done. Complexes 1 and 2 show very weak antiferromagnetic (OOC-CH(2)-CH(2)-COO) and ferromagnetic coupling (mu-H(2)O). Complex 3 also shows antiferromagnetic (syn-syn mu-OCO), and ferromagnetic coupling (mu-O of the -COO group). Complex 4 with two types (syn-syn and syn-anti) of binding modes of the carboxylate group shows strong antiferromagnetic interaction.  相似文献   

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