A new tripodal ligand containing ferrocenyl and hydrazone groups was synthesized by the condensation of ferrocenylcarbonylhydrazine with tris {[2 (2 formylphenyl)oxo]ethyl}amine and characterized by elemental analyses...A new tripodal ligand containing ferrocenyl and hydrazone groups was synthesized by the condensation of ferrocenylcarbonylhydrazine with tris {[2 (2 formylphenyl)oxo]ethyl}amine and characterized by elemental analyses, IR and 1H NMR. It is expected to be an important ligand to react with transition metals to give functional coordination complexes with interesting physical chemical properties. Studies on its reactions and properties are in progress.展开更多
Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.C... Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.展开更多
A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(w...A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142～150 S·cm 2·mol -1 , indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75～120 ℃ and 120～210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.展开更多
A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4&...A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4·2.7H_2O in acetonitrile, and characterized by X-raycrystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a =1.16891(4) nm, b= 2.06671(6) nm, c = 2.48185(7) nm, β= 97.8560(10)°, R = 0.0487, wR =0.1211. Theresults of structure analysis indicate that each TITMB ligand coordinates three metal atoms and inturn each Cd(Ⅱ) atom with octahedral coordination geometry connects six nitrogen atoms of imidazolegroup from six different TITMB ligands to produce a 2D honeycomb network structure. There are a lotof water molecules linked by hydrogen bonds and occupied the channels formed intra- andinter-sheets.展开更多
A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by...A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by X ray crystal structure analysis. The result reveals that the Er 3+ is encapsulated by the three arms of the tripodal ligand, and nine coordinated by the bridged head nitrogen atom, all ether oxygen atoms and carbonyl oxygen atoms of the ligand, and two oxygen atoms of the bidentate picrate. The coordination polyhedron is a distorted mono-capped square antiprism.展开更多
An N-hydroxyl peptide unit of H-L-Pro-L-Ala-L-Ala-β-（BnO）Ala-OMe was synthesized by stepwise chain building method in solution. Then, based on nitrilotriacetic acid backbone and this N-hydroxyl peptide unit, a nove...An N-hydroxyl peptide unit of H-L-Pro-L-Ala-L-Ala-β-（BnO）Ala-OMe was synthesized by stepwise chain building method in solution. Then, based on nitrilotriacetic acid backbone and this N-hydroxyl peptide unit, a novel chiral tripodal ligand P as an analogue of desferrichrome, has been synthesized. In neutral pH, ligand P formed stable tri（hydroxamato）- iron（Ⅲ） complexes which showed a maximum absorptiota （∑max=2750 M^-lcm^-1） at 422 nm in UV-Vis spectra. The characteristic absorption spectra are similar to those of natural trihydroxamate-type siderophores.展开更多
Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been establi...Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been established by X-ray crystallography The Cu (Ⅱ) atom is in a distorted trigonalbipyranddal environment with three benzimindazole N atoms of ntb defining the equatorial plane, oneandne N atom of ntb, and one O atom of the carboxylate group of isonicotinate occupying the axialpositions.展开更多
A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystal...A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.展开更多
A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by I...A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378（5）, b = 14.334（5）, c = 15.012（6） , α = 107.637（5）, β = 95.635（3）, γ = 92.825（4）°, V = 2720.7（17） 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F（000） = 1052, T = 293（2） K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles （Mn3）, each of which is bridged by a μ3-oxygen atom.展开更多
The La(III) complex with a new amide-type tripodal ligand, 2,2,2-nitrilotris{[(2-benzylaminoformyl)- phenoxy]ethyl}amine (L), was synthesized and characterized by X-ray crystallographic analysis. Crystal data: C48H55....The La(III) complex with a new amide-type tripodal ligand, 2,2,2-nitrilotris{[(2-benzylaminoformyl)- phenoxy]ethyl}amine (L), was synthesized and characterized by X-ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic, space group, P21/n, a=1.0644(3) nm, b=2.3889(5) nm, c=2.1917(5) nm, b=90.65, V=5.573(2) nm3, Z=1, Dc=1.394 gcm-3, R1=0.0487, wR [I>2s(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two-dimensional sheet of 4.82 networks is assembled by metal-ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three-connected nodes.展开更多
A trinuclear Zn(II) complex Zn3(L)2(Cl)2(OSO3)2(H2O)2·2H2O (1) (L=N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine) was synthesized by reaction of ligand L with ZnSO4·7H2O at pH=9 in air. The comple...A trinuclear Zn(II) complex Zn3(L)2(Cl)2(OSO3)2(H2O)2·2H2O (1) (L=N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine) was synthesized by reaction of ligand L with ZnSO4·7H2O at pH=9 in air. The complex has been characterized by elemental analysis, FTIR and X-ray single crystal diffraction. It reveals that the crystal of complex 1 belongs to monoclinic C2/c space group, a=3.516 9(7) nm, b=0.676 57(14) nm, c=1.502 2(3) nm, β=110.955(4)°, V=3.337 9(12) nm3, Z=4. In complex 1, two ligands L bridge three Zn(II) centers to form trinuclear structure which was further connected by hydrogen bonding to form two-dimensional structure. CCDC: 609515.展开更多
文摘A new tripodal ligand containing ferrocenyl and hydrazone groups was synthesized by the condensation of ferrocenylcarbonylhydrazine with tris {[2 (2 formylphenyl)oxo]ethyl}amine and characterized by elemental analyses, IR and 1H NMR. It is expected to be an important ligand to react with transition metals to give functional coordination complexes with interesting physical chemical properties. Studies on its reactions and properties are in progress.
基金Project (No. 973602311) supported by the Tianjin Natural Science Foundation of China
文摘 Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.
文摘A tripodal ligand, tris{2 [N (pyridine methanoyl)amino]ethyl}amine(L), and its complexes with rare earth nitrates were synthesized. These new complexes with the general formula of Ln(NO 3) 3·L·6H 2O(where Ln=La, Nd, Eu, Tb, Y) were characterized by elemental analysis, IR spectra, thermal analysis, 1 H NMR spectra, molar conductivity and luminescent spectra. All the complexes are stable in air and their conductances in acetonitrile solution lie in the range of 142～150 S·cm 2·mol -1 , indicating 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the C=O groups take part in coordination to the metal ions. The thermal behaviour of Eu complex shows that the weight losses at 75～120 ℃ and 120～210 ℃ correspond to the loss of four lattice water molecules and that of two coordinated water molecules, respectively. The luminescent spectra of the complexes of Eu(Ⅲ) and Tb(Ⅲ) were investigated in methanol.
文摘A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4·2.7H_2O in acetonitrile, and characterized by X-raycrystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a =1.16891(4) nm, b= 2.06671(6) nm, c = 2.48185(7) nm, β= 97.8560(10)°, R = 0.0487, wR =0.1211. Theresults of structure analysis indicate that each TITMB ligand coordinates three metal atoms and inturn each Cd(Ⅱ) atom with octahedral coordination geometry connects six nitrogen atoms of imidazolegroup from six different TITMB ligands to produce a 2D honeycomb network structure. There are a lotof water molecules linked by hydrogen bonds and occupied the channels formed intra- andinter-sheets.
文摘A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by X ray crystal structure analysis. The result reveals that the Er 3+ is encapsulated by the three arms of the tripodal ligand, and nine coordinated by the bridged head nitrogen atom, all ether oxygen atoms and carbonyl oxygen atoms of the ligand, and two oxygen atoms of the bidentate picrate. The coordination polyhedron is a distorted mono-capped square antiprism.
文摘An N-hydroxyl peptide unit of H-L-Pro-L-Ala-L-Ala-β-（BnO）Ala-OMe was synthesized by stepwise chain building method in solution. Then, based on nitrilotriacetic acid backbone and this N-hydroxyl peptide unit, a novel chiral tripodal ligand P as an analogue of desferrichrome, has been synthesized. In neutral pH, ligand P formed stable tri（hydroxamato）- iron（Ⅲ） complexes which showed a maximum absorptiota （∑max=2750 M^-lcm^-1） at 422 nm in UV-Vis spectra. The characteristic absorption spectra are similar to those of natural trihydroxamate-type siderophores.
文摘Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been established by X-ray crystallography The Cu (Ⅱ) atom is in a distorted trigonalbipyranddal environment with three benzimindazole N atoms of ntb defining the equatorial plane, oneandne N atom of ntb, and one O atom of the carboxylate group of isonicotinate occupying the axialpositions.
基金supported by the National Natural Science Foundation of China (No.20771083)
文摘A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.
基金Supported by the National Natural Science Foundation of China (Nos. 20633020 and 20973172)the National Basic Research Program of China (No. 2009CB220009)+1 种基金the Natural Science Foundation of Fujian Province (No. 2008J0175)the Fujian Province Youth Foundation (No. 2007F3112)
文摘A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378（5）, b = 14.334（5）, c = 15.012（6） , α = 107.637（5）, β = 95.635（3）, γ = 92.825（4）°, V = 2720.7（17） 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F（000） = 1052, T = 293（2） K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles （Mn3）, each of which is bridged by a μ3-oxygen atom.
基金Project Supported by the National Natural Science Foundation of China (No. 29871014).
文摘The La(III) complex with a new amide-type tripodal ligand, 2,2,2-nitrilotris{[(2-benzylaminoformyl)- phenoxy]ethyl}amine (L), was synthesized and characterized by X-ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic, space group, P21/n, a=1.0644(3) nm, b=2.3889(5) nm, c=2.1917(5) nm, b=90.65, V=5.573(2) nm3, Z=1, Dc=1.394 gcm-3, R1=0.0487, wR [I>2s(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two-dimensional sheet of 4.82 networks is assembled by metal-ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three-connected nodes.
文摘A trinuclear Zn(II) complex Zn3(L)2(Cl)2(OSO3)2(H2O)2·2H2O (1) (L=N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine) was synthesized by reaction of ligand L with ZnSO4·7H2O at pH=9 in air. The complex has been characterized by elemental analysis, FTIR and X-ray single crystal diffraction. It reveals that the crystal of complex 1 belongs to monoclinic C2/c space group, a=3.516 9(7) nm, b=0.676 57(14) nm, c=1.502 2(3) nm, β=110.955(4)°, V=3.337 9(12) nm3, Z=4. In complex 1, two ligands L bridge three Zn(II) centers to form trinuclear structure which was further connected by hydrogen bonding to form two-dimensional structure. CCDC: 609515.
