A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurall...A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.展开更多
Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-...Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.展开更多
Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic ...Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.展开更多
The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is u...The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.展开更多
The 2D porous copper（Ⅰ） complex with 1,3-dicyanobenzene （DCB）, [Cu（DCB）2]（PF6）（Me2CO） 1, exhibits channels along axis c, in which one molecule acetone and one anion PF6 per formula unit are included respect...The 2D porous copper（Ⅰ） complex with 1,3-dicyanobenzene （DCB）, [Cu（DCB）2]（PF6）（Me2CO） 1, exhibits channels along axis c, in which one molecule acetone and one anion PF6 per formula unit are included respectively. The reversible incorporation of guest acetone and acetonitrile, as well as the anion exchange from PF6^- to BF4^- or CF3SO3^-, was investigated by thermogravimetric （TG） analysis, ^1H NMR spectra and/or infrared absorption spectroscopy. Additionally, the incorporation of benzene and toluene into complex 1 was also discussed. Complex 1 exhibited size selectivity for guest inclusion or anion exchange.展开更多
The title compound,[Cu4I4（C4H8N4）4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851（10）,b=9.3697（5）,c=19.8034（10...The title compound,[Cu4I4（C4H8N4）4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851（10）,b=9.3697（5）,c=19.8034（10）A,V=3374.3（3）A^3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm^3,μ=6.183 mm^-1,F（000）=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections（I〉2σ（I））.The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.展开更多
Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been s...Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.展开更多
A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoc...A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].展开更多
A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type l...A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.展开更多
The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crys...The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).展开更多
The title compound [Cu2（μ2-dppm）2（MeCN）2（μ2-MeCN）]（ClO4）2·MeCN （dppm = bis（diphenylphosphino）methane） has been prepared and characterized. It crystallizes in the monoclinic system,space group P21/n,...The title compound [Cu2（μ2-dppm）2（MeCN）2（μ2-MeCN）]（ClO4）2·MeCN （dppm = bis（diphenylphosphino）methane） has been prepared and characterized. It crystallizes in the monoclinic system,space group P21/n,with a = 11.904（6）,b = 20.755（11）,c = 24.744（13）A,β = 98.226（12）°,C58H56Cl2Cu2N4O8P4,Mr = 1258.93,V = 6051（5） A^3,Z = 4,Dc = 1.382 g/cm^3,μ = 9.52 mm^-1,F（000） = 2592,R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I 〉 2σ（I）. Each Cu（I） center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands,one nitrogen atom from a terminally coordinated acetonitrile molecule,and another nitrogen atom from a μ2-acetonitrile molecule. The two Cu（I） centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a ＇chair-like＇ configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm.展开更多
One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR a...One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, spa...The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.展开更多
A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characteriz...A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.展开更多
A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b =...A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.展开更多
The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for th...The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex： triclinic, space group PI^-, a = 1.06853（12）, b = 1.30740（16）, c = 1.49546（17） nm, α= 101.791（2）,β = 103.413（2）, γ = 105.815（2）°, V= 1.8736（4） nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7（000） = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate： molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.展开更多
基金Project supported by the National Natural Science Foundation of China（No. 20331010）.
文摘A two-coordinate copper（Ⅰ） complex, Cu2（bipy）（H2L）2 （1） （H3L=cyanuric acid, bipy=4,4＇-bipyridyl）, which exhibits strong photoluminescence, has been synthesized under hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in the monoclinic space group P21/n, with cell parameters： Mr= 539.42, a= 13.4806（5）A↑°, b=4.5234（2） A↑°, c= 15.4952（8）A↑°,β = 105.526（3）°, V=910.39（7）A↑°^3, Z=2 and μ=3.52 mm^ -1. In the structure the two Cu（Ⅰ） ions are bridged by bipy to form a two-coordinate copper（Ⅰ） dimer. The adjacent dimer units are connected by hydrogen bonding interactions, resulting in 1D zigzag chains along the c axis. 1 emits intense yellow light when excited with UV light.
基金the State Key Project (No. 2005CCA06800)the NSFC/RGC Joint Research Foundation (50418010)
文摘Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.
基金supported by the National Natural Science Foundation of China (No.20872057)
文摘Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.
基金the support from the National Natural Science Foundation of China(No.20172038).
文摘The six multiimidazole copper（Ⅰ） complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu（Ⅰ）2（3b）（MeCN）2]（CIO4）2 and O2 under mild conditions, which are found to be more efficient than that already reported.
文摘The 2D porous copper（Ⅰ） complex with 1,3-dicyanobenzene （DCB）, [Cu（DCB）2]（PF6）（Me2CO） 1, exhibits channels along axis c, in which one molecule acetone and one anion PF6 per formula unit are included respectively. The reversible incorporation of guest acetone and acetonitrile, as well as the anion exchange from PF6^- to BF4^- or CF3SO3^-, was investigated by thermogravimetric （TG） analysis, ^1H NMR spectra and/or infrared absorption spectroscopy. Additionally, the incorporation of benzene and toluene into complex 1 was also discussed. Complex 1 exhibited size selectivity for guest inclusion or anion exchange.
基金supported by the National Natural Science Foundation of China (20873150, 20821061, and 50772113)Chinese Academy of Sciences (KJCX2-YW-M05)+1 种基金the Natural Science Foundation of Fujian Province (2006F3135, 2006F3141, 2007HZ0001-1)the Fund of Fujian Key Laboratory of Nanomaterials (2006L2005)
文摘The title compound,[Cu4I4（C4H8N4）4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851（10）,b=9.3697（5）,c=19.8034（10）A,V=3374.3（3）A^3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm^3,μ=6.183 mm^-1,F（000）=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections（I〉2σ（I））.The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.
基金Supported by the National Natural Science Foundation of China(NSFC 21102102)
文摘Two new Cu（Ⅰ） complexes [CuCl（3-PyOH）（PPh_3）_2]（1） and [Cu_2（μ-Cl）_2（4-Stpy）（Ph_3P）_3]（2）（PyOH = hydroxypyridine; stpy = styrylpyridine） with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945（7）, b = 37.266（2）, c = 10.9461（7） A, β = 116.0750（10）°, V = 3625.3（4） A^3, Z = 4, D_c = 1.350 Mg/cm^（-3）, μ = 0.801 mm^（-1）, F（000） = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections（I 〉 2σ（I））, R（all data） = 0.0413, wR（all data） = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290（3）, b = 20.388（5）, c = 24.092（6） A, β = 102.028（4）°, V = 5424（2） A^3, Z = 4, D_c = 1.428 Mg/cm^（-3）, μ = 1.016 mm^（-1）, F（000） = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections（I 〉 2σ（I））, R（all data） = 0.0716, wR（all data） = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu（I） complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.
文摘A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].
文摘A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.
文摘The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).
基金supported by the NNSFC (20801047)the Foundation of Xuzhou Normal University (07XLA07, KY2007039 and XGG2007034)the Qinglan Project (08QLT001)
文摘The title compound [Cu2（μ2-dppm）2（MeCN）2（μ2-MeCN）]（ClO4）2·MeCN （dppm = bis（diphenylphosphino）methane） has been prepared and characterized. It crystallizes in the monoclinic system,space group P21/n,with a = 11.904（6）,b = 20.755（11）,c = 24.744（13）A,β = 98.226（12）°,C58H56Cl2Cu2N4O8P4,Mr = 1258.93,V = 6051（5） A^3,Z = 4,Dc = 1.382 g/cm^3,μ = 9.52 mm^-1,F（000） = 2592,R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I 〉 2σ（I）. Each Cu（I） center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands,one nitrogen atom from a terminally coordinated acetonitrile molecule,and another nitrogen atom from a μ2-acetonitrile molecule. The two Cu（I） centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a ＇chair-like＇ configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm.
基金Supported by the Hunan Provincial Department of Science and Technology Project (2009FJ3101)
文摘One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金This work was financially supported by the Natural Science Foundation of Fujian province
文摘The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.
基金This work was supported by the NSF for Distinguished Young Scientist of China (20425104) and the NSF of Fujian Province (A0420002, 2005I017)
文摘A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.
基金Project(21001118)supported by National Natural Science Foundation of ChinaProject(12JJ3016)supported by Natural Science Foundation of Hunan Province,China
文摘A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.
基金Project supported by the Foundation of Education Committee of Hunan Province (06C187), Fund for Distinguished Young Cadreman of Hengyang Normal University (2006) and Science and Technology Bureau Foundation of Hengyang (2005Cg10-23)
文摘The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex： triclinic, space group PI^-, a = 1.06853（12）, b = 1.30740（16）, c = 1.49546（17） nm, α= 101.791（2）,β = 103.413（2）, γ = 105.815（2）°, V= 1.8736（4） nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7（000） = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate： molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.
