铜配合物[CuL_2Cl_2]·4H_2O的合成和晶体结构(L=3-乙基-4-对甲氧苯基-5-(2-吡啶基)-1,2,4-三氮唑)

A new copper(Ⅱ)complex,[CuL_2Cl_2]·4H_2O,[L=3-ethyl-4-(p-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole],was synthesized and characterized by X-ray crystallography and infrared spectroscopy.The complex crystallizes in triclinic system with space group P(1),α=0.843 9(7)nm,b=0.965 5(8)nm,c=1.093 6(8)nm,α=84.026(19)°,β=82.33(2)°,γ=89.167(19)°,V=0.878 3(12)nm~3,Z=1 with final R=0.033 8.The copper atom lies in a distorted octahedral environment with two bidentate chelating ligands(L)in the equatorial plane and two Cl~- ions in the axial positions.The ligand L coordinates via one triazole nitrogen and one pyridine nitrogen atom.The molecules are stabilized by intermolecular hydrogen bonds in the crystal lattice.CCDC:705817.     

Synthesis,Crystal Structure and DNA-binding Properties of a New Copper（Ⅱ） Schiff Base Complex

A new asymmetric bidentate copper(Ⅱ) complex,CuL 2(HL=2-((E)-(4-bromophenylimino)methyl)-6-bromo-4-chlorophenol),has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218(3),b=9.355(3),c=13.449(4),β=108.722(4)°,V=1336.8(6)3,Z=2,Dc=2.008 g/cm 3,μ(MoKα)=7.024 mm-1,F(000)=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections (I>2σ(I)).The central copper(Ⅱ) is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA(CT-DNA),presumably via a partial intercalative mode.The intrinsic binding constant of the Cu(Ⅱ) complex with DNA is 7.335×10 3 M-1.     

Synthesis and Crystal Structure of a Novel Dinuclear Copper（Ⅱ） Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper(Ⅱ) complex [CuL(NO3)]2·2MeOH was obtained by the coordination reaction of Cu(NO3)2·3H2O with ligand HL (HL=N-(methyl-2-benzimidazol- methylidene)-2-hydroxyaniline). The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535(3), b=10.009(3), c=10.666(4) , α=104.303(4), β=100.105(4), γ=115.917(4)o, V=839.0(5) 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F(000)=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper(Ⅱ) complex units [CuL(NO3)]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper(Ⅱ) units.     

Synthesis, Structure and Luminescence of Zn4.5Cu3 Heteronuclear Coordination Polymer Comprising Macrocyclic Oxamide and 5-Sulfosalicylic Ion

<正>The complex[Zn_(4.5)(SSA)_3(CuL)_3(H_2O)_6]_n was synthesized and structurally determined,where SSA is fully deprotonated 5-sulfosalicylic acid(CuL,H_2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca- 7,13-dien).The title complex crystallized in the triclinic system with space group P1,a=1.19788(17) nm,b=1.4253(2) nm,c=2.2890(4) nm,α=90.211(2)°,β=93.076(2)°,γ=90.600(2)°.The complex displayed a 1D ladderlike chain.All these 1D chains were further interlinked via hydrogen bonds,resulting in a 2D architecture.The luminescent property of the compound was also discussed.     

Synthesis,Crystal Structure and Magnetic Behavior of a Novel Cd(Ⅱ) Complex with Four Nitroxide Radicals

A novel diamagnetic-metal Cd(Ⅱ) complex with four nitroxide radicals[Cd(IM4Py)4Cl2](IM4Py=2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) was synthesized and characterized by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction.The complex crystallized in triclinic space group P1 with a=0.93285(14) nm,b=1.16827(18) nm,c=1.3660(2) nm,α=112.759(2)°,β=104.524(2)°,γ=92.008(3)°,V= 1.3143(3) nm3,Z=1,Dc=1.335 g/cm3,the final R1=0.0423 and wR2=0.1009.In the title complex,each Cd(Ⅱ) ion adopting a distorted octahedral geometry is coordinated by two Cl-anions and four pyridyl-N atoms from four IM4Py ligands.The magnetic measurements show the weak antiferromagnetic interactions between the nitroxide radicals.     

2-(1H-1,2,4-三氮唑)乙酸Cu(Ⅱ)配合物的水热合成、晶体结构及性质

A copper(Ⅱ) complex [CuL2] [L=2-(1H-1,2,4-triazol-1-yl)acetic acid] has been synthesized by means of hydrothermal method, and characterized by elemental analysis, IR spectra and X-ray diffraction. Crystal data for this complex: monoclinic, space group P21/n, a=0.481 3(2) nm, b=1.151 1(6) nm, c=0.993 9(5) nm, β=100.528(8)°, V=0.541 4(5) nm3, Z=2, F(000)=318, Dc=1.937 g·cm-3, Final GooF=1.109, R1=0.027 6, wR2=0.075 6. The crystal structure shows the copper(Ⅱ) atom is six-coordinated by two triazole nitrogen atom and four carboxylate group oxygen atom from four distinct L- ligand, thereby forming a 2D network structure. The cyclic voltammetric behavior of the complex was described.     

A Novel Layered Complex with Rhomboidal Channels:Hydrothermal Synthesis, Crystal Structure, and Properties of Cu(4,4′-bipy)2(H2PO4)2(H2O)2 (bipy=bipyridine)

The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)2(H2PO4)2(H2O)2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)2(H2PO4)2(H2O)2 units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c-axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm. Crystal data: triclinic, space group P-1, a=1.0253(2) nm, b=1.4501(3) nm, c=0.79715(16) nm, α=97.91(3)°, β=90.99(3)°, γ=85.54(3)°, V=1.1703(4) nm3, Z=2, R=0.0892, wR=0.2451.     

Hydrothermal Synthesis,Crystal Structure,Spectrum Properties and Quantum Chemical Calculation of a Trinuclear Copper（Ⅱ） Complex with 3-（Pyridin-2-yl）-1,2,4-triazole

A three-dimensional framework copper(Ⅱ) coordination polymer with copper carbonate basic and 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) has been hydrothemally synthesized.The complex (2,C14 H10 CuN8 ·3H2 O) crystallizes in tetragonal,space group P4 2 /n,a=2.08581(12),b=2.08581(12),c=0.72331(4) nm,M r=761.73,V=3.1468(3) nm 3,Dc=1.608 g/cm 3,Z=4,F(000)=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.     

Synthesis, crystal structure and forming mechanism of two novel copper (Ⅱ) α-methacrylate complexes with benzimidazole

Two copper (Ⅱ) a-methacrylate complexes with benzimidazole, Cu [CH_2=C( CH_3)-COO]_2(C_7H_6N_2)_2(1) and Cu_2 [CH_2=C(CH_3)-COO]_4(C_7H_6N_2)_2 (2), have been prepared and characterized by elemental analyses, IR and electronic reflectance spectroscopies. The single crystal X-ray diffraction study of the two complexes shows that complex 1 has a square planar configuration, while complex 2 has a binuclear cage structure. The crystal structural analyses show that both complexes 1 and 2 are monoclinic, with space group P2_1/c, a=0.924 16(8) nm, b=1.233 02(13) nm, c =0.989 1(3) nm, β=91.912(13)°, D_c=1.386 g/cm~3, Z=2, R=0.033 9 for the former; and a=0.905 7(2) nm, b=2.252 1(5) nm, c=1.623 5(4) nm, β=90.11(2)°, D_c =1.411 g/cm~3 , Z=4, R=0.056 8, Cu-Cu=0.266 21 nm for the latter. Different structural types of complexes 1 and 2 were produced simultaneously in the reaction of copper (Ⅱ) α-methacrylate with benzimidazole in methanol solution. The forming mechanism of the complexes has been summarized.     

四(4-乙烯基吡啶)硝酸铜(Ⅰ)配合物的结构、电化学和热稳定性能研究(英文)

The title complex Cu(Vpy)NO3 (Vpy=4-vinylpyridine) has been synthesized and structurally characterized by X-ray single crystal diffractometry. The complex crystallizes in triclinic system, P1 space group with the cell parameters of a=1.004 2(2) nm, b=1.631 7(3) nm, c=1.887 7(4) nm, α=81.54(2)°, β=77.44(2)°, γ=79.39(2)°, V= 2.948 9(11) nm3, Z=4, and Dc=1.230 g·cm-3, the final R1=0.075 2, wR2=0.139 1. The complex crystallizes with two molecules in the asymmetric unit. Each Cu(Ⅰ) ion is coordinated by four N atom from the Vpy ligands and one O atoms from the nitrate anion, resulted in a square pyramidal geometry. The electrochemical studies reveal that redox of Cu2+/Cu+ in the complex is a quasi-reversible process. CCDC: 736638.     

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5-Benzenetetracarboxylato Trivalent Anion

The title complex [(phen)2Cu(Htcb)Cu(phen)2]H3tcb(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.     

Crystal structure and fluorescence spectrum of the complex [Eu(Ⅲ)(TTA)_3(phen)]

The title complex Eu(Ⅲ)(TTA)3(phen) (where TTA= thenoyltrifluoroacetone monoanion; phen = 1,10-phenanthroline) has been synthesized in mixed solvents of acetone and ethanol (1:1 volume ratio) and its crystal structure has been determined by X-ray diffraction. The complex crystals are triclinic, space group P1(#2) with cell dimensions of a = 1.3241 (2) nm, 6 = 1.5278(4) nm, c = 0.9755(3) nm, α = 92.49 (2)°, β=102.57(2)°, γ = 91.62(2)°, V=1.9268(8) nm3, Z = 2, μ(Mo Kα) = 18.77 cm-1, Dx = 1.720 g/cm3. The coordination geometry of Eu atom is a distorted square antiprism, and the encapsulated structure that can meet the structural requirement of the typical europium luminescent sensor. The fluorescence spectrum suggests that the complex is a strong photoluminescent material.     

Hydrothermal Synthesis, Crystal Structure, Spectrum and Electrochemical Analysis of the Copper（Ⅱ） Coordination Polymer

The three-dimensional framework copper(Ⅱ) coordination polymer with basic copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole has been hydrothermally synthesized. It crystallizes in monoclinic space group P21/c, with a = 1.20860(3), b = 1.29581(2), c = 1.67863(3) nm, β = 116.0280(2)°, C21H12Cu3N12, Mr = 623.05, V = 2.36230(9) nm3, Dc = 1.752 g/cm3, Z = 4, F(000) = 1236, GOOF = 1.037, the final R = 0.0408 and wR = 0.1141. Every unit cell contains three copper atoms and three 3-(pyridin-2-yl)-1,2,4-triazole ligands. Every central Cu(Ⅱ) ion is coordinated by four nitrogen atoms of the 3-(pyridin-2-yl)-1,2,4-triazole ligands, forming a distorted tetrahedron. The title complex exhibits an intense photoluminescence at room temperature with the maximum emission at 392 nm. The cyclic voltametric behavior of the complex shows that the electron transfer in electrolysis reaction is irreversible.     

二维网状Pd(Ⅱ)配合物的合成、晶体结构及电化学性质(英文)

A novel palladium(Ⅱ) complex [Pd(H2bpdc)Ala]Cl·3H2O (where H2bpdc is 2,2′-bipyridine-3,3′-dicar- boxylic acid and Ala is L-alanine) has been synthesized and characterized by IR spectra and elemental analysis. The crystal structure of the complex has been determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic system, space group P1 with a=0.685 5(2) nm, b=0.988 4(4) nm, c=1.349 6(4) nm, α=98.375(8)°, β= 97.900(15)°, γ=90.118(15)°, V=0.895 9(5) nm3, Z=2. In the molecule, Pd(Ⅱ) atom is four-coordinated and located at the centre of a planar quadrangle. The complex is assembled via intramolecular π-π stacking interactions and hydrogen bonds, which forms 2D network. The cyclic voltammetric behavior of the complex was also investigated.     

Synthesis,Structure and Photophysical Properties of a Dinuclear Copper (Ⅰ) Complex Based on Phosphinopyridine and Diphosphine Mixed-ligands

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,M_r=1507.42,D_c=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(λ_max=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.     

单核铜配合物Cu(C_(16)H_(13)N_2OS_2)_2的合成、晶体结构和生物活性(英文)

A planar copper complex Cu(L)2,HL=(E)-benzyl-2-(4-formylbenzylidene)-Hydrazinecarbodithioate,has been prepared via the template effect of copper ion. Crystal structure of the complex was determined by X-ray singlecrystal diffraction analysis. The crystal data for this complex:Orthorhombic,space group Pbcn,a=2.250 0(14) nm,b=1.660 0(11) nm,c=0.830 4(5) nm,V=3.102(3) nm3,Z=4,μ=1.011 mm-1,Dc=1.478 g·cm-3,F(000)=1 420,R1= 0.050 1,wR2=0.087 2 (observed reflections with I2σ(I)) and R1=0.129 1,wR2=0.100 9 (all reflections) GOF= 1.011. In the compound,Cu(Ⅱ) atom is four-coordinated with two N atoms and two S atoms from two bidentate ligands and located in the inversion center. The preliminary bioassay indicates that the complex exhibits distinct antitumor activity.     

阶梯状配位聚合物[Cu(μ_3-I)INH]_n的合成、晶体结构及其热稳定性研究

The complex [Cu( μ3-I)INH]n has been synthesized in DMF solution with INH, CuI, where INH=isoniazid. The crystal structure of the complex has been determined by X-ray diffraction single crystal structure analysis. The crystal belong to monoclinic system, space group P21/c. The cell parameters are: a=1.009 48(10) nm, b=0.467 51(5) nm, c=1.992 62(19) nm, β=101.413 0(10)°, and V= 0.921 81(16) nm3, Z=4, μ(Mo Kα)=5.674 mm-1, F(000)=616.0, R1=0.031 6, wR2=0.082 5 [I2σ(I)]. The copper(Ⅰ) atom locates in a distorted coordination tetrahedron. The copper(Ⅰ) atoms bridged by μ3-I to form a band stair-like chain, and INH occupying the remaining coordination site of the approximately tetrahedral. The stair-like chains extend along b axis. The results of TG analysis show the title complex was stable under 200℃.     

Synthesis, structure and characterization of the trinuclear copper (Ⅰ) complex [Cu_3(μ_3Br)_2(dppm)_3]Br

The novel trinuelear copper(I) complex [Cu3(μ3-Br)2(dppm)3]Br has been obtained by reaction of bis(diphenyl-phosphino)methane (dppm) with cupric bromide. The title complex was characterized by single-crystal X-ray analysis, elemental analysis, molecular weight determination, 31P NMR and its conductivity was also measured. The [Cu3(dppm)3Br2] cation consists of a triangular array of copper atoms, with dppm ligands (Ph2PCH2PPh2) bridging each edge of the triangle and two triply bridging Br groups bound to the two faces of the Cu3 unit. Crystallographic data: monoclinic, space group P21/c, a = 1.4739(4) , b = 1.7708(5), c = 2.8395(8) nm, β= 97.16(3)°, V = 7.353nm3, Z = 4,F(000)= 3296, Dcalc = 1.472 g/cm3, μ= 26.478 cm-1, R = 0.06, Rw = 0.08, 4654 reflections observed with I > 3σ(I).     

Synthesis,Crystal Structure and Photoluminescence of a TADF Cuprous Complex

A cuprous mononuclear copper complex [Cu(adpypz)CH3CNPPh3]BF4·CH2Cl2(1, adpypz = 9,9-dimethyl-10-(6-(3-phenyl-1H-pyrazol-1-yl)pyridin-2-yl)-9,10-dihydroacridine) was synthesized and characterized by Elemental Analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in triclinic, space group P1 with a = 11.3388(4), b = 13.4569(4), c = 16.2561(6) ?, α = 97.154(3), β = 92.187(3), γ = 114.119(4)°, V = 2235.38(13) ?3, Z = 2, Mr = 967.12, Dc = 1.437 g/cm~3, F(000) = 996, μ = 2.62 mm~(–1), GOOF = 1.031, the final R = 0.0417, and w R = 0.1024 for 8043 observed reflections with I 2σ(I). The Cu(I) atoms in the complex are four-coordinated and adopt a tetrahedral coordination geometry. In the solid state, the complex exhibits bluish-green photoluminescence with emission peaks λmax = 492 nm(1), lifetimes 235 μs and quantum yields(ф = 0.279) at room temperature. The studies of varied temperature emission spectra and decay behaviours of the complex indicate that the complex displays thermally activated delayed fluorescence(TADF) at room temperature. The results of the experimental and DFT calculations suggest that the emission in the solid state originates from the ILCT excited states.     

Syntheses, Structural Characterization of Fe and Ni Complexes with Polypyrazolyl Borate Ligand ： Fe [ HB （pz） 3 ] 2 and Ni [ HB （pz） 3 ] 2

Fe(Ⅱ) complex Fe[HB(pz)3]2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)3]2(compound 2) have been obtained by the reaction of MCI2(M=Fe and Ni) with NaHB(pz)3 in MeOH. The two complexes(compounds 1 and 2) were characterized by IR, NMR, elemental analysis and X-ray diffraction. Compound 1 crystallizes in space group P21/c with a=1.224(3) nm, b=1.161(2) nm, c=1.648(3) nm, β=107.62(15)°, V=2.233(8) nm3, Z=2. Compound 2 crystallizes in space group P21/c with a=0.97926(18) nm, b=1.7423(3) nm, c=1.3156(2) nm, β=97.055(16)°, V=2.2277(7) nm3, Z=4. The results of X-ray structural analyses show that both compounds 1 and 2 are monomeric neutral, possessing a similar coordination mode and a similar structure around the metal centers. The related spectral characterizations, steric effects and binding properties are discussed.