A new binuclear copper(Ⅱ) complex [Cu2(Hpt)2(TNCA)2(H2O)2]·4 H2O(1) has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid(TNCA) and 3-(pyridin-2-yl)-1,2,4-...A new binuclear copper(Ⅱ) complex [Cu2(Hpt)2(TNCA)2(H2O)2]·4 H2O(1) has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid(TNCA) and 3-(pyridin-2-yl)-1,2,4-triazole(Hpt). It crystallizes in the triclinic space group P-1, with a = 8.8199(18), b = 14.278(3), c = 15.269(3) A, α = 76.21(3)o, β = 81.07(3)o, γ = 76.07(3)o, V = 1802.7(6) A3, Dc = 1.636 g/cm3, Z = 2, F(000) = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of the Cu(1) ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu(Ⅱ) ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.展开更多
A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8...A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8), b = 9.4830(8), c = 12.262(1) ? = 81.079(5), b = 80.620(4), g = 78.960(4), V = 924.4(1) 3, Z = 1, C34H46Cu2Fe2N2O8, Mr = 849.51, Dc = 1.526 g/cm3, l(MoK) = 0.71073 ? ?= 1.954 mm-1, F(000) = 438, R = 0.0297 and wR = 0.0901. Both cyclopentadienyl rings in each dmaf (dmaf = (dimethylaminomethyl)ferrocene, Fe(C5H5)- [C5H4CH2N(CH3)2]) have an eclipsed conformation. The binuclear molecule has a crystallographic centrosymmetry; four acetates and two Cu atoms form a cage structure with the distance between two neighboring Cu atoms of 2.655(1) .展开更多
A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffracti...A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).展开更多
A binuclear copper(I) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space...A binuclear copper(I) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167(3), b = 21.209(4), c =20.680(4)A°, β = 103.93(3)°, C32H28CuN3O3P2, Mr = 628.05, Z = 8, μ = 0.868 mm^-1, V = 6031 (2) ,A°^3,F(000) = 2592, De= 1.383 g/cm^3, R = 0.0593 and wR = 0.1736. A total of 5297 independent reflections were collected, of which 3503 were observed with 1 〉 2σ(/). The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole. In the coordination sphere, the bond lengths of Cu-P(1) and Cu-P(2) are 2.2607(17) and 2.2503(16) A°,respectively and the P-Cu-P bond angle is 127.26(6)°.展开更多
A novel bis (phenoxo) bridged binuclear copper ( II) complex with dissimilar coordination environments was synthesized and characterized by spectroscopies and X-ray crystallography. It crystallized in the monoclinic...A novel bis (phenoxo) bridged binuclear copper ( II) complex with dissimilar coordination environments was synthesized and characterized by spectroscopies and X-ray crystallography. It crystallized in the monoclinic system with space group C2/c, a=2. 241 1(2) nm, b=1. 834 2 (2) nm, c=1.877 9(2) nm, β=122.861(2)°, V=6.484 3(11) nm3, Z=8. Itconsistsof two unsymmetrical Cu (Ⅱ ) centers bridged by two phenolic oxygen atoms to yield a Cu2O2 core with the Cu-Cu separation of 0. 310 2 nm, in which Cul and Cu2 ions exhibit distorted N2O3 and N3O2 square pyramidal geometries, respectively.展开更多
The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was ...The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.展开更多
The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calcula...The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)-Au(Ⅰ) interaction were also discussed.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
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
The title complex, Cu 2(O 2CCH 2Cl) 4 OC(NH 2)CH 3 2, crystallizes in space group P2 1/a with a=7.616(4), b=18.665(5), c=7.949(5) , β=106.29(5)°. V=1084(1) 3, Z=2, M r=619.19, D c =1.896 g/...The title complex, Cu 2(O 2CCH 2Cl) 4 OC(NH 2)CH 3 2, crystallizes in space group P2 1/a with a=7.616(4), b=18.665(5), c=7.949(5) , β=106.29(5)°. V=1084(1) 3, Z=2, M r=619.19, D c =1.896 g/cm 3; μ =25.05 cm -1 and F(000)=620.00, R =0.045 and R w =0.054 for 1807 observable reflections. X ray crystal structure analysis revealed that two Cu atoms are bridged by four chloroacetate groups, and the acetamine ligands are bonded by O(carboxide) to the terminal Cu atoms of each dimeric unit. The coordination geometry of Cu atom is a distorted octahedral configuration. The distance between the two Cu atoms is 2.648(1) .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
Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only ...Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.展开更多
Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized thr...Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized through elemental analyses, ICP, IR(4000-200 cm^(-1), CsI disc.), ^(31)P-NMR spectra. Their electronic conductivities, oxidation and reduction potentials were measured. Preliminary studies show that both of the two complexes have chlorobridging and phosphorus-bridging structures.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
A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, t...A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, the complex can efficiently cleavage pBR322 DNA with a rate constant kobs of 1.35×10-4 s-1. The cleavage occurred by a non-oxidative mechanism showing activity to be dependent on pH.展开更多
Three new binuclearcopper( ) complexesbridged by dithio- oxamidate(dto) group or biscyclohexanone oxalyldihydrazone (BCO) [Cu2 (en) 2 (dto) ](Cl O4) 2 .3H2 O (1)、[Cu2(dien) 2 (dto) ](Cl O4) 2 .2 H2 O (2 ) and [Cu2 (b...Three new binuclearcopper( ) complexesbridged by dithio- oxamidate(dto) group or biscyclohexanone oxalyldihydrazone (BCO) [Cu2 (en) 2 (dto) ](Cl O4) 2 .3H2 O (1)、[Cu2(dien) 2 (dto) ](Cl O4) 2 .2 H2 O (2 ) and [Cu2 (bipy) 2 (BCO) (Cl O4) 2 ](Cl O4) 2 (3) ,where en , bipy and dien denote ethylenediamine,2 ,2′- bipyridyl and diethylentriamine respectively, were synthesized and characterized by elemental analysis,IR,electronicspectra and variable temperature magnetic susceptibility. Variable temperature (4. 0 - 30 0 K ) magnetic susceptibility data for the complexes show that there exists the antiferromagnetic exchange interaction between the two copper( ) ionswith J(cm-1 ) valuesof- 0 .4 6 2 (1)、- 1.0 3 (2 ) and - 6 .86 (3) . The preliminary study of the electrochemical characteristicsof complex (3) was also carried out.展开更多
基金Supported by the Scientific Research Found of Hunan Provincial Education Department of China(17A049,17C0226)Industry and Research Key Project of Hengyang City(2017KJ155,2017KJ193)Doctoral Scientific Research Foundation of Hengyang Normal University(17D01)
文摘A new binuclear copper(Ⅱ) complex [Cu2(Hpt)2(TNCA)2(H2O)2]·4 H2O(1) has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid(TNCA) and 3-(pyridin-2-yl)-1,2,4-triazole(Hpt). It crystallizes in the triclinic space group P-1, with a = 8.8199(18), b = 14.278(3), c = 15.269(3) A, α = 76.21(3)o, β = 81.07(3)o, γ = 76.07(3)o, V = 1802.7(6) A3, Dc = 1.636 g/cm3, Z = 2, F(000) = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ2-η^1:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of the Cu(1) ion is CuO2N3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu(Ⅱ) ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.
基金The work was supported by the Provincial Education Foundation of Fujian (JA99135) the Test Foundation of Fuzhou University and the foundation of the Department of Chemistry Fuzhou University
文摘A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8), b = 9.4830(8), c = 12.262(1) ? = 81.079(5), b = 80.620(4), g = 78.960(4), V = 924.4(1) 3, Z = 1, C34H46Cu2Fe2N2O8, Mr = 849.51, Dc = 1.526 g/cm3, l(MoK) = 0.71073 ? ?= 1.954 mm-1, F(000) = 438, R = 0.0297 and wR = 0.0901. Both cyclopentadienyl rings in each dmaf (dmaf = (dimethylaminomethyl)ferrocene, Fe(C5H5)- [C5H4CH2N(CH3)2]) have an eclipsed conformation. The binuclear molecule has a crystallographic centrosymmetry; four acetates and two Cu atoms form a cage structure with the distance between two neighboring Cu atoms of 2.655(1) .
文摘A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).
基金This work was supported by the National Natural Science Foundation of China (No. 20271017) and Henan Provincial Innovation Foundation (No. 0421001300)
文摘A binuclear copper(I) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167(3), b = 21.209(4), c =20.680(4)A°, β = 103.93(3)°, C32H28CuN3O3P2, Mr = 628.05, Z = 8, μ = 0.868 mm^-1, V = 6031 (2) ,A°^3,F(000) = 2592, De= 1.383 g/cm^3, R = 0.0593 and wR = 0.1736. A total of 5297 independent reflections were collected, of which 3503 were observed with 1 〉 2σ(/). The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole. In the coordination sphere, the bond lengths of Cu-P(1) and Cu-P(2) are 2.2607(17) and 2.2503(16) A°,respectively and the P-Cu-P bond angle is 127.26(6)°.
基金the Guangdong Provincial Natural Science Foundation (Grant No. 970167).
文摘A novel bis (phenoxo) bridged binuclear copper ( II) complex with dissimilar coordination environments was synthesized and characterized by spectroscopies and X-ray crystallography. It crystallized in the monoclinic system with space group C2/c, a=2. 241 1(2) nm, b=1. 834 2 (2) nm, c=1.877 9(2) nm, β=122.861(2)°, V=6.484 3(11) nm3, Z=8. Itconsistsof two unsymmetrical Cu (Ⅱ ) centers bridged by two phenolic oxygen atoms to yield a Cu2O2 core with the Cu-Cu separation of 0. 310 2 nm, in which Cul and Cu2 ions exhibit distorted N2O3 and N3O2 square pyramidal geometries, respectively.
基金Supported by the Natural Science Foundation of Zhejiang Province(No. 2 0 2 137)
文摘The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.
文摘The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)-Au(Ⅰ) interaction were also discussed.
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.
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The title complex, Cu 2(O 2CCH 2Cl) 4 OC(NH 2)CH 3 2, crystallizes in space group P2 1/a with a=7.616(4), b=18.665(5), c=7.949(5) , β=106.29(5)°. V=1084(1) 3, Z=2, M r=619.19, D c =1.896 g/cm 3; μ =25.05 cm -1 and F(000)=620.00, R =0.045 and R w =0.054 for 1807 observable reflections. X ray crystal structure analysis revealed that two Cu atoms are bridged by four chloroacetate groups, and the acetamine ligands are bonded by O(carboxide) to the terminal Cu atoms of each dimeric unit. The coordination geometry of Cu atom is a distorted octahedral configuration. The distance between the two Cu atoms is 2.648(1) .
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).
文摘Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.
文摘Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized through elemental analyses, ICP, IR(4000-200 cm^(-1), CsI disc.), ^(31)P-NMR spectra. Their electronic conductivities, oxidation and reduction potentials were measured. Preliminary studies show that both of the two complexes have chlorobridging and phosphorus-bridging structures.
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.
文摘A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, the complex can efficiently cleavage pBR322 DNA with a rate constant kobs of 1.35×10-4 s-1. The cleavage occurred by a non-oxidative mechanism showing activity to be dependent on pH.
文摘Three new binuclearcopper( ) complexesbridged by dithio- oxamidate(dto) group or biscyclohexanone oxalyldihydrazone (BCO) [Cu2 (en) 2 (dto) ](Cl O4) 2 .3H2 O (1)、[Cu2(dien) 2 (dto) ](Cl O4) 2 .2 H2 O (2 ) and [Cu2 (bipy) 2 (BCO) (Cl O4) 2 ](Cl O4) 2 (3) ,where en , bipy and dien denote ethylenediamine,2 ,2′- bipyridyl and diethylentriamine respectively, were synthesized and characterized by elemental analysis,IR,electronicspectra and variable temperature magnetic susceptibility. Variable temperature (4. 0 - 30 0 K ) magnetic susceptibility data for the complexes show that there exists the antiferromagnetic exchange interaction between the two copper( ) ionswith J(cm-1 ) valuesof- 0 .4 6 2 (1)、- 1.0 3 (2 ) and - 6 .86 (3) . The preliminary study of the electrochemical characteristicsof complex (3) was also carried out.