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1.
王丹  刘世雄 《结构化学》2006,25(12):1461-1464
1 INTRODUCTION Binuclear copper(II) carboxylate complexes have been studied extensively, and most of them are fami- liar binuclear molecule Cu2(RCOO)4L2 with four same bridges[1~5]. However, only a few copper(II) car- boxylate complexes with mixed bridges have been reported, i.e., they have common formulaCu2(R1C- OO)2(R2COO)2L2, such as Cu2(μ- C9H11O4)2(μ-CH3C- OO)2(H2O)2[6],Cu2(μ-PTMMC)2(μ-CH3COO)2(H2O)2[7, 8] and[Cu2(μ-O2CCH3)2(μ-O2CCF3)2(H2O)2]?2CH3CO2H[9…  相似文献   

2.
The hydrothermal reaction of copper chloride dihydrate and 5,5-dimethyl-imi-dazolidine-2,4-dione with a mole ratio of 1:1 in acetonitrile resulted in the formation of a new acetate-bridged dinuelear copper complex, [C2H6ON]2[Cu2Cl2(μCH3COO)4]. Protonated aeetamide in enolic form and acetic acid were yielded by the hydrolysis of aeetonitrile under hydrothermal condition. The title complex (C12H24Cl2Cu2N2O10) was charactetized by X-ray single-crystal diffraction, IR spectrum, elemental and electrochemical analysis. It crystallizes in the monoclinie system, space group P21/c with a = 8.2980(14), b = 14.358(2), c = 12.0010(2) A,β= 130.620(3)°, V= 1085.3(2)A3, Dc = 1.696 g/am3, Mr = 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.  相似文献   

3.
IntroductionExchange coupledpolynuclearcopper(II)complex esareofspecialinterestduetotheirinvolvementinbio logicalprocessesandininorganicmaterials .1,2 Theinti materelationshipbetweenthespincouplingandthemolecularstructurehasfosteredtheemergenceofmolec ular…  相似文献   

4.
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.  相似文献   

5.
1INTRODUCT1ONFormode1ingcompoundsofcertaincopper-containingenzymes,theinvestigationofdinuclearcoppercomplexeshasattractedtheattentionofinorganicandbiologicchemistst1i.Actingasoxygentransportproteinsforinvertebrates,oxyhemocyanin(oxyHc)hasadinuclearcoppersitewithaCu-Cuseparationofca.3.6A[2'3i(Fig.1).In1984,Karlinetal-[4ireportedthesynthesisofadinuclearcopper(I)com-plexwithabidentateligand.Thecomplexreactswithdioxygenquasireversibly,whichproducesaperoxodinuclearcopper(I)complex(Nallo=8O3…  相似文献   

6.
7.
XIE  Yong-Shu ZHU  Yu 等 《中国化学》2002,20(3):292-295
A mixed-ligand copper(Ⅱ) complex[Cu2(phen)2(HL^1)2]-(ClO4)2(1) was synthesized.X-ray analyses reveal that 1 has a bis(μ2-phenoxo)-bridged dicopper(Ⅱ) structure.2D hydrogen-bonded network is formed utilizing the N-H,O-H and C-H groups of the (HL^1) ligands (H2L^1=N-(2-hydroxybenzyl)ethanolamine),the C-H groups of the phenanthrolines and the perchlorate anions.Variable temperature magnetic properties of 1 have shown comparatively weak antiferromagnetic interactions with respect to the bridge angles, which have been ascribed to the unfavorable overlaps of the magnetic orbitals fo the highly distorted copper coordination polyhedra and the pyramidal distortions at the phenoxo oxygen atoms.  相似文献   

8.
IntroductionDimericcopper(II)carboxylatescontainingavarietyofoxygenandnitrogen donorligandshavebeenextensivelyinvestigatedandtheirpreparations ,magneticandspectralpropertieshavebeenreviewed .1 5Differentkindsofcopper(II)carboxylateadductshavebeensynthesizedandalsodinuclearcopper(II)complexeshavebeenearlystud iedasusefulmodelstoestablishmagneto structuralcorre lationsforspinexchangebetweenmetalions .Inparticu lar,theoccurrenceofdicopperionsattheactivesiteofthevariousformsoftheoxygencarrierpro…  相似文献   

9.
Compounds [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) (I) and Ag3(CF3COO)3(CH3CN)2(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) Å3, Z= 8, R 1= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) Å3, Z= 2, R 1= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.  相似文献   

10.
One novel copper(Ⅱ) complex, [Cu(NAA)2(bim)2]·H2O (1, HNAA = a-naphthylacetic acid, bim = benzimidazole) has been synthesized and characterized by X-ray single-crystal diffraction analysis, elemental analysis, and IR spectrum. It crystallizes in monoclinic, space group C2/c with a = 1.15969(12), b = 1.9757(2), c = 1.45763(16) nm, β = 104.712(2)°, V = 3.2298(6) nm3, Z = 4, C38H32N4O5Cu, Mr = 688.22, Dc = 1.418 g/cm-3, μ = 0.729 mm-1, S = 1.039, F(000) = 1428, the final R = 0.0380 and wR = 0.0912 for 2849 unique reflections. In 1, two carboxylate and two benzimidazole ligands coordinate to the central Cu(Ⅱ) atom by a bidentate chelate mode. Interesting, reversible thermochromic properties of 1 can be observed and investigated by thermal analysis method.  相似文献   

11.
俞雯思  黄春花  黄细河 《结构化学》2021,40(2):175-181,145
Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH3CN)4BF4afforded a dinuclear Cu(I)complex[Cu2(dpppy)2(dppm)(CH3CN)](BF4)2·3CH2Cl2(1).Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail.It crystallizes in triclinic space group P1-with a=13.0834(8),b=13.5568(8),c=21.8544(11)?,α=76.090(5)°,β=80.803(5)°,γ=64.582(6)°,V=3391.3(3)?3,Z=2,Mr=1507.42,Dc=1.476 g/cm3,F(000)=1532,GOOF=1.071,the final R=0.0700 for 9041 observed reflections with I>2σ(I)and wR=0.2063 for all data.The complex contains a Cu2-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement.In the crystalline phase,complex 1 exhibits bright bluish-green photoluminescence(λmax=488 nm)with high quantum yield(?=0.57)at room temperature.It is still a relatively high emission quantum yield(?=0.36)in doped PMMA thin film with 20 wt%dopant of complex 1.The emission peaks of 1 in dichloromethane solution and doped PMMA(20 wt%)thin films are 510 and 494 nm,respectively,showing a very slight bathochromic shift compared to that in crystalline phase.This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.  相似文献   

12.
T A dinuclear cadmium complex[Cd2(phen)2(C14H11O3)4(CH3CH2OH)]·(CH3OH)·(H2O)has been synthesized with benzilic acid and 1,10-phenanthroline by hydrothermal method.The crystal structure was determined bv X-ray diffraction with crystal parameters as follows:triclinic system with space group P-1,α=1.21298(10),b=1.32586(1 1),c=2.4815(2)nm,α=76.2630(10),β=81.4500(10),γ=69.1700(10)°V=3.6143(5)nm3,Dc=1.438g/cm3,Z=1,F(000)=1600,the final GOOF=0.937,R=0.0521 and wR=0.1328.In the title complex,the dinuclear structure is defined by carboxyl oxygen atoms adopting a monodentate bridged coordination mode.The coordination environment of Cd(Ⅱ)ion is CdO4N2,giving a distorted octahedral coordination geometry.TG analysis shows that the title complex is stable under 140℃.  相似文献   

13.
<正>A new kind of Cu (II) complex [Cu(tpmb)2Cl2]·CH3OH·H2O (tpmb = 1,3,5-tri(2-pyrimidinyl)sulfanylmethyl-2,4,6-trimethylbenzene) was synthesized, and its structure has been determined by X-ray single-crystal diffraction. It crystallizes in the triclinic, space group P 1 with a = 8.8397(2), b = 13.327(3), c = 13.926(3) A, α = 63.27(3), β = 86.96(3), r = 80.68(3)°, V = 1445.6(5) A3, C49H51Cl2CuN12O2S6, Mr= 1166.82,Z=1, F(000) = 604, Dc = 1.340 g/cm3, μ = 0.735 mm-1, R = 0.0545 and wR = 0.1575 for 4521 observed reflections (I > 2σ(I)). X-ray analysis reveals that the Cu (II) ion is coordinated by two Cl- anions and two nitrogen atoms from different pyrimidine groups, forming a square structure.  相似文献   

14.
Mononuclear copper( Ⅰ ) complex [Cu(PPh3)2(BH4)] has been synthesized by ligand replacement reaction in methanol and characterized by elemental analyses, molecular weight determination, IR spectra and X-ray single crystal analysis,its conductivity has also been measured. The crystal is monoclinic, space group C2/c, a =24.776(4), b=9.173(7), c=15.564(2)A; β=116.10(1)°, V=3176.73 A3, Z =4, F(000)=1256, μ(MoKα)=8.11 cm-1, Dc=1. 26 g/cm3, M=602.79, R=0. 039, Rw= 0. 050. The results show that PPh3 coordinates as monodentate ligand to the Cu ( Ⅰ ) atoms, and BH4 behaves as a bidentate ligand in the prepared complex.The central copper atom belongs to tetrahedron coordination geometry.  相似文献   

15.
Heterocyclic -aminovinyl ketones (HL) and the copper complex CuL2 are synthesized and studied by IR and 1H NMR spectroscopies. The crystal structure of one of the tautomeric HL molecules is determined by X-ray diffraction analysis. The crystals are triclinic: a = 9.261(6) Å, b = 9.448(6) Å, c = 11.310(5) Å, = 96.74(5)°, = 99.46(5)°, = 93.60(5)°, space group P . The compound has the form of a ketoamine tautomer. The structure contains intramolecular and intermolecular hydrogen bonds. The latter link the molecules into the center-symmetric dimers.  相似文献   

16.
A new copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191(11),b = 12.8883(13),c = 16.1114(16) ?,α = 70.8090(10),β = 80.568(2),γ = 77.440(2)o,V = 1984.3(4) ?3,Dc = 1.551 g/cm3,Z = 2,F(000) = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η1:η0 3-carboxylate groups of MNA2-.The coordination environment of Cu(Ⅱ) ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.  相似文献   

17.
The construction of molecular-based crystalline solids using coordination polymer has become a very active research field in recent years,not only due to their intriguing structural motifs,but also due to their potential applications in optical,electronic and magnetic materials1,2.Many of the most interesting coordination polymers are based on polycarboxylate ligands,such as maleate3,malonate4,1,4-benzenedicarboxylate5,1,3,5-benzenetricar-boxylate6and1,2,4,5-benzenetetracarboxylate7,which have …  相似文献   

18.
The title complex (C26H18CuN2O6, Mr=517.96) has been synthesized by the reaction of α-furanacrylic acid with 1,10-phenanthroline (phen) in the solvent mixture of water and methanol. Crystal data: monoclinic, space group C2/c with a=2.2927(4), b=1.01248(18), c=1.05061(18) nm, β=111.188(3)°, V=2.274(7) nm3, Dc=1.513 g/cm3, Z=4, F(000)=1060,μ=1.007mm-1, R=0.0320 and wR=0.0781. The crystal structural analysis shows that the copper atom is coordinated with four oxygen atoms from two α-furacrylic acids and two nitrogen atoms from 1,10-phenanthroline, giving a distorted octahedral coordination geometry. The result of electrochemical analysis shows that the electron transfer in the electrode reaction is quasi-reversible.  相似文献   

19.
20.
A four-coordinate mononuclear cuprous complex [Cu(ac1m)POP]BF_4·0.5(C_6H_(14))· 0.5(C_2H_5OH)(1, ac1 m = 2-(2-ethoxyphenyl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-(dipenylphosphino)phenyl]ether) was synthesized and characterized by elemental analysis, NMR, UV-vis, cyclic voltammetry and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group P2_1/c with a = 17.0546(19), b = 15.4650(17), c = 23.685(2) ?, β = 104.007(11)°, V = 6061.1(12) ?~3, Z = 4, M_r = 1171.46, D_c = 1.284 g/cm~3, F(000) = 2432, μ = 1.50 mm~(–1), GOOF = 1.070, the final R = 0.059 and wR = 0.1640 for 8952 observed reflections with I 2σ(Ⅰ). Compound 1 is composed of a BF4-anion and a [Cu(ac1m)POP]~+ cation. The Cu(Ⅰ) ion adopts a tetrahedral coordination geometry defined by two nitrogen and two phosphorous atoms. The complex exhibits yellow luminescence with maximum emission peaks at 546 nm, lifetimes 15.1 μs and quantum yields(ф = 0.130) at room temperature. The complex displays thermally activated delayed fluorescence(TADF) at room temperature, which is proved experimentally and theoretically. And the organic light-emitting diode(OLED) with 1 as the light emitting material has the maximum current efficiency of 5.86 cd/A and the highest brightness of 3215 cd/m~2.  相似文献   

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