A new heterometallic complex {[Cu（pic）2（H2O）2][Cd2（Hdipic）2（H2O）2Cl2]}n （Mr = 1007.73） has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes...A new heterometallic complex {[Cu（pic）2（H2O）2][Cd2（Hdipic）2（H2O）2Cl2]}n （Mr = 1007.73） has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group PI^- with a = 5.8397（4）, b = 9.8664（7）, c = 14.1739（10） °A, α= 82.0150（10）, β = 80.4540（10）, γ= 82.3570（10）°, Z= 1, V= 792.47（10）°A^3, Dc = 2.112 g/cm^3,μ（MoKα） = 2.247 mm^-1, F（000） = 495, the final R = 0.0232 and wR = 0.0644 for 2748 observed reflections （I〉 2σ（I））. In the complex, seven-coordinated·Cd ions form a zigzag chain based on the alternated dinuclear Cd units. The neutral [Cu（pic）2（H2O）2] units are located at the centers of the inter space and fasten to the 1-D chain by hydrogen bonds.展开更多
The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imidazolidine,-2,4-dione with a mole ratio of 1：1 in acetonitrile resulted in the formation of a new acetate-bridged dinuclear copper complex, [...The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imidazolidine,-2,4-dione with a mole ratio of 1：1 in acetonitrile resulted in the formation of a new acetate-bridged dinuclear copper complex, [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]. Protonated acetamide in eaolie form and acetic acid were yielded by the hydrolysis of acetonitrile under hydrothennal condition. The rifle complex （C12H24Cl2Cu2N2O10） was characterized by X-ray single-crystal diffraction, IR spectrum, elemental and electrochemical analysis. It crystallizes in the monoclinic system, space group P21/c with a = 8.298004）, b = 14.358（2）, c = 12.0010（2） A^°, β= 130.620（3）°, V = 1085.3（2） A^°^3, Dc = 1.696 g/cm^3, 34, = 554.31, Z = 2, F（000） = 564 and μ = 2.254 mm^-1. The crystal structure consists of a tetraacetate-bridging dinulcear copper complex anion [Cu2Cl2（μ-CH3COO）4]^2-, with the chlorine anions in the axial positions, and two protonated acetamide cations [C2H6ON]^＋, which were connected through hydrogen bonds to form a three-dimensional infinite network.展开更多
A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassiu...A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassium acetate buffer.X-ray structural analyses show that compounds 1-5 are isomorphic and consist of[Ln(GeW11O39)2] 13-polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure.The 1D chain further connects into the 3D framework byπ-πinteractions with neighboring bpy groups.The magnetic susceptibility data indicate that anti-ferromagnetic coupling between the neighboring Cu2+ions in the structure and the rare earth ions affects magnetic property of the structure.展开更多
The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and therma...The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and thermal analysis. Its crystal structure was determined by single crystal X ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The cell parameters are: a=0.82510(11)nm, b=0.68870(9)nm, c=2.3007(3)nm, β =100.847(2)° , V=1.2840(3)nm3, Z=2, Dc=1.742Mg· m- 3, μ (MoKα )=1.723mm- 1, F(000)=684. The structure was refined to final R1=0.0267, wR2=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu2O2 core features. The ligand N (2,4 dihydroxybenzalidene) o aminobenzoic acid dianion is μ 2 tridentate, chelating one copper? ion via one nitrogen, one hydroxy oxygen atom and one carboxylate oxygen atom, and the hydroxy oxygen atom simultaneously coordinates to the other copper? ion of the dimer. In the structure the copper? ion rendered four coordination in a distorted square planar geometry structure. CCDC: 212695.展开更多
A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively w...A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively was synthesized and its DNA binding behavior was studied by photophysical methods. It has been found that calf thymus DNA could result in significant decrease both in electronic absorption and fluorescent emission of the complex. The fluorescence quenching by ferrocyanide could be reduced to some extent for the complexin presence of DNA. These facts suggest that this dicopper?complex binds to double helix DNA by partial intercalation.展开更多
A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes i...A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes in the triclinic system, space group P1 with cell parameters a=0.846 0(17) nm, b=1.289 5(3) nm, c=1.452 7(3) nm, α=77.42(3)°, β=79.11(3)°, γ=87.08(3)°, and V=1.518 8(6) nm3. The dinuclear complex shows potential DNA cleavage activity at micromolar concentration in the presence of H2O2 and exhibits higher nuclease efficiency than mononuclear complex [Cu(dipic)(H2dipic)]·H2O. Without external reductants, the added H2O2 may contribute to the generation of hydroxyl radicals that result in DNA strand scission.CCDC:291786.展开更多
The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126...The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126(4)nm; β =113.89(2)° ; Mr=587.52 (C16H28Cu2N8O8); V=1.1299(5)nm3. The copper atom lies in a distorted square pyramidal environment. The four equatorial donors are four nitrogen atoms from bidentate chelate dimethylglyoxime anion ligands. The oxygen atom from the dimethylglyoxime ligand acts as a bridging atom occupying the apical position of the symmetry related copper atom in the dimer structure. The two dimethylglyoximes bridge two copper atoms to form a six member Cu2O2N2 ring, respectively. The thermal gravity (TG) data indicate that the compound [Cu2(Hdmg)4] undergoes two exothermic reactions with loss of the organic ligand to give residue CuO. CCDC: 208729.展开更多
The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction....The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.展开更多
基金The work was supported by the National Natural Science Foundation of China (No. 50572024)
文摘A new heterometallic complex {[Cu（pic）2（H2O）2][Cd2（Hdipic）2（H2O）2Cl2]}n （Mr = 1007.73） has been synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group PI^- with a = 5.8397（4）, b = 9.8664（7）, c = 14.1739（10） °A, α= 82.0150（10）, β = 80.4540（10）, γ= 82.3570（10）°, Z= 1, V= 792.47（10）°A^3, Dc = 2.112 g/cm^3,μ（MoKα） = 2.247 mm^-1, F（000） = 495, the final R = 0.0232 and wR = 0.0644 for 2748 observed reflections （I〉 2σ（I））. In the complex, seven-coordinated·Cd ions form a zigzag chain based on the alternated dinuclear Cd units. The neutral [Cu（pic）2（H2O）2] units are located at the centers of the inter space and fasten to the 1-D chain by hydrogen bonds.
基金Supported by the High Technical Foundation of Jiangsu Province (BG2007047)the Key Project for Fundamental Research and Natural Science Foundation of Jiangsu Provincial Educational Commission (07KJA150011 and 05KJB150003)
文摘The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imidazolidine,-2,4-dione with a mole ratio of 1：1 in acetonitrile resulted in the formation of a new acetate-bridged dinuclear copper complex, [C2H6ON]2[Cu2Cl2（μ-CH3COO）4]. Protonated acetamide in eaolie form and acetic acid were yielded by the hydrolysis of acetonitrile under hydrothennal condition. The rifle complex （C12H24Cl2Cu2N2O10） was characterized by X-ray single-crystal diffraction, IR spectrum, elemental and electrochemical analysis. It crystallizes in the monoclinic system, space group P21/c with a = 8.298004）, b = 14.358（2）, c = 12.0010（2） A^°, β= 130.620（3）°, V = 1085.3（2） A^°^3, Dc = 1.696 g/cm^3, 34, = 554.31, Z = 2, F（000） = 564 and μ = 2.254 mm^-1. The crystal structure consists of a tetraacetate-bridging dinulcear copper complex anion [Cu2Cl2（μ-CH3COO）4]^2-, with the chlorine anions in the axial positions, and two protonated acetamide cations [C2H6ON]^＋, which were connected through hydrogen bonds to form a three-dimensional infinite network.
文摘A series of inorganic-organic hybrids K2NamH9-m[{Ln(GeW11O39)2}{Cu2(bpy)2(μ-ox)}]·nH2O(bpy=2,2-bipyridine and ox= oxalate;Ln=La,Nd,Sm,Eu,Gd;n=19,17,22,20,19;m=4,4,4,9,2)were isolated after reacting in a potassium acetate buffer.X-ray structural analyses show that compounds 1-5 are isomorphic and consist of[Ln(GeW11O39)2] 13-polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure.The 1D chain further connects into the 3D framework byπ-πinteractions with neighboring bpy groups.The magnetic susceptibility data indicate that anti-ferromagnetic coupling between the neighboring Cu2+ions in the structure and the rare earth ions affects magnetic property of the structure.
文摘The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and thermal analysis. Its crystal structure was determined by single crystal X ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The cell parameters are: a=0.82510(11)nm, b=0.68870(9)nm, c=2.3007(3)nm, β =100.847(2)° , V=1.2840(3)nm3, Z=2, Dc=1.742Mg· m- 3, μ (MoKα )=1.723mm- 1, F(000)=684. The structure was refined to final R1=0.0267, wR2=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu2O2 core features. The ligand N (2,4 dihydroxybenzalidene) o aminobenzoic acid dianion is μ 2 tridentate, chelating one copper? ion via one nitrogen, one hydroxy oxygen atom and one carboxylate oxygen atom, and the hydroxy oxygen atom simultaneously coordinates to the other copper? ion of the dimer. In the structure the copper? ion rendered four coordination in a distorted square planar geometry structure. CCDC: 212695.
文摘A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively was synthesized and its DNA binding behavior was studied by photophysical methods. It has been found that calf thymus DNA could result in significant decrease both in electronic absorption and fluorescent emission of the complex. The fluorescence quenching by ferrocyanide could be reduced to some extent for the complexin presence of DNA. These facts suggest that this dicopper?complex binds to double helix DNA by partial intercalation.
文摘A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes in the triclinic system, space group P1 with cell parameters a=0.846 0(17) nm, b=1.289 5(3) nm, c=1.452 7(3) nm, α=77.42(3)°, β=79.11(3)°, γ=87.08(3)°, and V=1.518 8(6) nm3. The dinuclear complex shows potential DNA cleavage activity at micromolar concentration in the presence of H2O2 and exhibits higher nuclease efficiency than mononuclear complex [Cu(dipic)(H2dipic)]·H2O. Without external reductants, the added H2O2 may contribute to the generation of hydroxyl radicals that result in DNA strand scission.CCDC:291786.
文摘The structure of [Cu2(Hdmg)4] (Hdmg=dimethylglyoxime anion) has been determined by X ray crystallography. It is monoclinic, space group P21/n, with Z=2. The lattice parameters: a=0.71601(14)nm; b=1.7044(3)nm; c=1.0126(4)nm; β =113.89(2)° ; Mr=587.52 (C16H28Cu2N8O8); V=1.1299(5)nm3. The copper atom lies in a distorted square pyramidal environment. The four equatorial donors are four nitrogen atoms from bidentate chelate dimethylglyoxime anion ligands. The oxygen atom from the dimethylglyoxime ligand acts as a bridging atom occupying the apical position of the symmetry related copper atom in the dimer structure. The two dimethylglyoximes bridge two copper atoms to form a six member Cu2O2N2 ring, respectively. The thermal gravity (TG) data indicate that the compound [Cu2(Hdmg)4] undergoes two exothermic reactions with loss of the organic ligand to give residue CuO. CCDC: 208729.
文摘The macrocyclic ligand(L) and its dinuclear copper(Ⅱ) and zinc(Ⅱ) complexes have been synthesized. The crystal structure of [Cu 2L(Him) 2](ClO 4) 4·2H 2O has been determined by single crystal X ray diffraction. It crystallizes in a monoclinic system, the space group P2 1/c , a =0.951 2(2) nm, b =2.010 4(4) nm, c =1.202 5(2) nm, β =98.89(3)°, V =2.271 9(8) nm 3, Z=2, D c=1.599 Mg/m 3 , F (000) = 876 , R =0.059 1, wR =0.173 3, GOF(F)=1.009. The copper(Ⅱ) atom is five coordinated with four nitrogen atoms of the macrocyclic ligand and one nitrogen atom of imidazole. The stepwise stability constants of the 1∶1 and 2∶1 molar ratios of Cu to L and Zn to L complexes were determined by potentiometric titration in KCl supporting electrolyte(0.100 mol/L) at 25 ℃. The results indicated that zinc(Ⅱ) ion can form hydroxide bridged dinuclear complex [Zn 2(OH)L] 3+ , while the copper(Ⅱ) ion can only form dinuclear complex 3+ with macrocyclic ligand.
