配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

混合配体配合物钯(Ⅱ)-联喹啉-苯乙基丙二酸根与DNA作用研究

The mixed ligand complex [Pd(biqu)(pmal)]·H₂O (where biqu is 2,2′-biquinoline, pmal is phenethylmalonate) has been synthesized and its interaction with sperm DNA was determined by fluorescent spectra、 UV-Vis spectra and CD-spectra. The binding constant (K_b) of the complex and sperm DNA is 1.26×10⁴ and its interaction with pBR322 plasmid DNA was also determined by gel electrophoresis. The results show that the complex interact with DNA mainly by intercalative mode.     

三种1,10-邻菲咯啉-铜(Ⅱ)-L-氨基酸配合物与DNA的相互作用

The Interaction of three complexes [Cu(phen)(Gly)(H₂O)]·ClO₄·2.5H₂O (1), [Cu(phen)(L-Val)(H₂O)]·ClO₄ (2) and [Cu(phen)(L-Ile)(H₂O)]·ClO₄ (3) (phen=1,10-phenanthroline, Gly=glycinate, L-Val=L-valinate, L-Ile=L-isoleucinate) with DNA have been investigated by electronic absorption spectroscopy, ethidium bromide(EB) fluorescence spectroscopy, viscosity and gel electrophoresis measurements. The intensity of maximal absorption peaks from absorption spectra are weakened with dropping DNA into the complexes. The emission intensity of EB-DNA systems in fluorescence spectroscopy have descended 50%, when the data of C_Cu / C_DNA is 30～40. Moreover, the viscosity of DNA increase and then decrease with the increasing of complexes. All of the results indicate that the interaction of complexes with DNA are partial intercalation, and the result of agarose gel electrophoresis show that the complexes can cleave pBR322 DNA in the present of H₂O₂ / vitamin C.     

[Mn(H2O)(phen)2(PAc)](ClO4)的合成、红外光谱及晶体结构

The complex [Mn(H₂O)(phen)₂(PAc)](ClO₄) was synthesized and investigated by elemental analysis, molar conductivity, IR spectrum and X-ray diffraction methods, where phen=1,10-phenanthroline and PAc=phenylac-etate group. The complex crystallizes in the triclinic space group,P1 , with a=0.9289(2)nm,b=1.2425(2)nm,c=1.4791(3)nm,α=114.34(3)°,β=91.25(3)°,γ=104.65(1)°,V=1.4893(4)nm³,Z=2,F(000)=686,D_c=1.489g·cm^-3,μ=0.589mm^-1. The Mn(Ⅱ) ion has a six-coordinate distorted-octahedral geometry with the four nitrogen atoms of two phen ligands,a coordinated-water oxygen atom, and a carboxylate oxygen atom of PAc^-. There is π-π stacking interaction between two phen rings from two neighbor molecules.     

配合物[Cu2(phen)2](SiW12O40)(H2O)7的合成、晶体结构及电化学分析

The title complex has been synthesized by the reaction of silicotungstic acid, 1,10-phenanthroline (phen) monohydrate and cupric acetate. The crystal structure belongs to triclinic system, space group P1 with a=1.158 46(15) nm, b=1.658 8(2) nm, c=1.664 4(2) nm, α=82.090(2)°, β=76.001(2)°, γ=86.531(2)°, and V=3.072 6(7) nm³, D_c=3.887 g·cm^-3, Z=2, F(000)=3 196. R₁=0.086 7, wR₂=0.185 8. The structure shows that the copper(Ⅱ) atom is coordinated with two nitrogen atoms from the one phen and three oxgygen atoms from three water, forming a distorted square-pyramid configuration The cyclic voltametric behavior of the complex is also reported. CCDC: 298807.     

配合物Cu(3，5-DMBA)2(phen)的合成、晶体结构及电化学性质

A copper(Ⅱ) complex Cu(3，5-DMBA)₂(phen) has been synthesized by self-assembly of 3，5-dimethylbenzoic acid， 1，10-phenanthroline and copper perchlorate. Crystal data for this complex: Monoclinic， space group C2/c with a=2.348 3(5) nm， b=0.984 4(2) nm， c=1.138 4(2) nm， β=103.02(3)°， V=2.563 9(9) nm³， D_c=1.404 g·cm^-3， Z=4， F(000)=1 124， final GooF=1.051， R₁=0.035 0， wR₂=0.099 8. The crystal structure shows that the copper atom is coordinated with two oxygen atoms from two 3，5-dimethylbenzoic acids and two nitrogen atoms from the 1，10-phenanthroline， forming a square-planar structure. The result of the cyclic voltametric behavior analysis shows that the electron transfer in electrode reaction is quasi-reversible. CCDC: 650387.     

配合物[Co(phen)2(m-chlorobenzoic acid)2·(H2O)]·(H2O)2的水热合成、晶体结构电化学分析

The title complex has been synthesized with m-chlorobenzoic acid, 1,10-phenanthroline and cobalt perchlorate anhydrous in the solvent mixture of water and methanol. Crystal data for this complex: triclinic, space group P1, a=0.870 7(3) nm, b=1.284 4(4) nm, c=1.692 9(5) nm; α=75.430(5)°, β=77.562(5)°, γ=86.346(5)°, V=1.789 4(9) nm³, D_c=1.456 g·cm^-3, Z=2, F(000)=806. Final GooF=1.065, R₁=0.068 4, wR₂=0.127 5. The crystal stru-cture shows that the Cobaly ion is coordinated with four nitrogen atoms from two 1,10-phenanthroline molecules and two oxygen atoms from one m-chlorobenzoic acid molecule and one water molecule respectively, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 619087.     

2,4,6-三甲基苯甲酸和1,10-邻菲啰啉双核铽配合物的合成和晶体结构

A binuclear terbium complex with 2,4,6-Trimethylbenzoate and 1,10-phenanthroline, [Tb₂(TMBA)₆(Phen)₂], has been synthesized (TMBA=2,4,6-Trimethylbenzoic acid and phen=1,10-phenanthroline) and characterized by IR, elemental analysis and X-ray diffraction methods. The title complex crystallizes in monoclinic system, space group P2₁/c with a=1.327 5(2) nm, b=2.817 9(5) nm, c=1.282 5(2) nm, β=116.692(3)°, V=4.286 2(13) nm³, Z=4，D_c=1.423 g·cm^-3. There are four bridged carboxylate groups of the 2,4,6-trimethylbenzoic acid bonded to the two terbium ions, each ions is also chelated with the two oxygen atoms of a molecule of the 2,4,6-trimethylbenzoic acid and the two nitrogen atoms of a 1,10-phenanthroline respectively, forming a 8-coordination distorted square antiprism. Average Tb-O and Tb-Ndistance of the two Tb(Ⅲ) ions are equal respectively. This shows the two terbium ions are in the same chemical enviorments. The complex emits intense green fluorescence under ultraviolet light. CCDC: 619215.     

新配合物[Cd(H2O)2(phen)2](PA)2的制备及晶体结构

The new compound was prepared by the reaction of Cd(ClO₄)₂·6H₂O,1,10-phenanthroline (phen)and picric acid (HPA)(ratio 1∶3∶2) in methanol-aqueous solution refluxing for 4 hours. The crystals used for X-ray analysis was obtained by slow evaporation of the solution at room temperature. The crystal compound is in triclinic with space group with a=1.1363(4)nm,b=1.2593(2)nm,c=1.3972(4)nm,α=93.97(2)?,β=100.84(3)?,γ=106.29(2)?,Z=2,V=1.8690(9)nm³,D_c=1.715g·cm^-3, μ(MoKα)=0.677mm^-1,F(000)=972,R=0.0907,wR=0.2240. In the complex, the Cd(Ⅱ) cation is octahedrally coordinated to two 1,10-phenanthroline ligands and two water molecules in cis disposition. As outer sphere, picrate anions are combined with inner by hydrogen bond and static electricity interaction.     

共平面的μ-S桥联（1，10-菲咯啉）钯(Ⅱ)双核配合物的晶体结构与π-π堆积

A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)₂Pd(phen)](NO₃)₂·2H₂O} (1) was synthesized and characterized by the ¹H NMR, element analysis and single crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=2.165 1(3) nm, b=1.291 4(2) nm, c=2.716 2(3) nm, β=111.987(3)°, and V=7.041 8(16) nm³, Z=8, R=0.054 4, wR=0.127 4. The X-ray crystal structure analysis revealed that two 1,10-phenanthroline palladium(Ⅱ) moieties were bridged by two n-propylmercapatan molecules in coplanar fashion with the dimensions of 1.55 nm×0.88 nm. The plane-to-plane distance of the complex 1 is 0.33 nm, which reveals strong aromatic-aromatic π-π interaction. CCDC: 292998.     

超分子三维氢键网络：{[Cu(phen)3](SO4)(H3PCA)2(8H2O)}的晶体结构

A new complex， {[Cu(phen)₃](SO₄)(H₃PCA)₂(8H₂O)}， was synthesized and structurally characterized by single-crystal X-ray analysis. The complex is composed of copper cations， sulfate anions， 1，10-phenanthroline， protocatechuic acid and lattice water molecules. The structure of H₃PCA， SO₄^2- and waters comprises packing of anionic three-dimensional network by hydrogen bonds with cavities. The complex can be considered as a model of host/guest supramolecule. The three-dimensional hydrogen-bonding network is the host species. The Cu(phen)₃²⁺ cations， guest species， occupied the cavities of the host. And the results demonstrate that the form of protocatechuic acid at pH< 1 should be free ligand. CCDC： 191733.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

双核铜(Ⅱ)-氟喹诺酮-邻菲咯啉混配配合物的合成、晶体结构和抗肿瘤活性

A new binuclear copper (Ⅱ) complex with 1,10-phen and fluoroquinolone ligands, [Cu₂(cfc)₂(phen)₂(pip)](NO₃)₂(CO)₂,was synthesized and its crystal structure was solved.The formula of the complex is C₂₈H₂₄ClCuFN₅O₇, and the crystallography data are as follows, triclinic, space group P1, a=0.80372(6)nm, b=0.94712 (7)nm, c=1.67826(13)nm, α=88.5650(10)°, β=80.9920(10)°, γ=70.2780(10)°, V=1.18722(6)nm³, Z=2, D=1.848g· cm^-3, F(000)=676. R₁=0.0627 and wR₂=0.1684 (I>2σ(I)). The copper atom is five- coordinate with square-based pyramidal geometry and involves two nitrogen atoms from phen, two oxygen atoms from cfc and one nitrogen atom from pip anion. The stacking effect between cfc and phen ligands from two neighboring molecules was observed. FT-IR spectrum of the complex was also discussed. Both ligand and complex were assayed against gram-positive and gram-negative bacteria by doubling dilutions method； the complex shows the same mini-mal inhibitory concentration (MIC) as the corresponding ligand against S. Aureus, E. Coli and M. Lutens bac-teria. The inhibitory effect of the ligand and complex on leukemia HL-60 cell line and liver cancer BEL-7402 cell line have been measured by using MTT (Methyl-Thiazol- Tetrozolium) and SRB (Sulphurhodamin B) assay meth-ods, respectively. The results indicated that the complex has strong inhibitory effect on HL-60 and BEL-7402 cell line. CCDC: 203964.     

配合物[Cu(PTA)(phen)2]·(PTA)·(H2O)4的合成、晶体结构及电化学性质

The title complex has been synthesized by using terephthalic acid (PTA), 1,10-phenanthroline (phen) and copper monohydrate. It crystallizes in monoclinic space group C2/c with a=2.959 0(2) nm, b=1.466 4(10) nm, c=1.764 3(12) nm, β=105.593(11)°, V=7.372(9) nm³, Dc=1.489 g·cm^-3, Z=8, F(000)=3 416, R₁=0.043 6, wR₂= 0.151 9. The crystal structure shows that the copper atom is coordinated with four nitrogen atoms from two phens and one oxygen atom from one terephthalic acid, forming a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 277047.     

顺式-二(硫氰酸根)·二氨合铂(Ⅱ)的合成、表征及其水溶液析出物质机制的探讨

Cis-diaminedithiocyanatoplatinum(Ⅱ) (cis-[Pt(SCN)₂(NH₃)₂]) was prepared and characterized through content analysis of Pt, MS, IR. The results show that the complex has cis configuration and the bond type of Pt and SCN^- is Pt-S. When the aqueous solution of the complex was stored for one week, an orange-yellow precipitation appeared, different from the complex with light yellow color. Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)₂(NH₃)₂], the linkage isomerism of cis-[Pt(SCN)₂(NH₃)₂]. The mechanism of the isomerism reaction is also discussed.     

十一烯酸邻菲咯啉铜(Ⅱ)配合物的合成、表征、晶体结构及与DNA作用

A copper(Ⅱ) complex Cu(C₁₁H₁₉O₂)₂(phen)(H₂O), (C11H19O₂=undecylenic acid, phen=1,10-phenanthroline), was synthesized and characterized by elemental analysis, IR and TG-DTG. Its crystal structure was determined by single crystal X-ray diffraction method. The complex, C₃₄H₄₈N₂O₅Cu, crystallizes in the triclinic system, space group P1. The interaction of complex with DNA was also studied by ethidium bromide (EB) fluorescence spectroscopy. CCDC: 729209.     

配合物[Sm(o-MOBA)3(phen)·H2O]2·4H2O的合成与晶体结构

The title complex [Sm(o-MOBA)₃(phen)·H₂O]₂·4H₂O has been synthesized by the reaction of SmCl₃·6H₂O with o-methoxybenzoic acid and 1,10-phenanthroline in 1∶3∶1 molar ratio. The crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic system, space group P1 with a=1.203(10) nm, b=1.293(10) nm, c=1.306(11) nm, α=64.50(10)°, β=81.93(10)°, γ=74.81(10)°. The molecular structure shows that the Sm³⁺ ion coordinates to nine atoms. The carboxylate groups are bonded to the samarium ion in three modes: monodentate, bidentate chelating, tridentate chelating-bridging. CCDC: 603740.     

[Cu(PTA)(Phen)2](p-MBA)(H6O)配合物的合成、晶体结构及电化学分析

The crystal structure of the title complex with the stoichiometric formula [Cu(PTA)(Phen)₂](p-MBA)(H₆O) (Phen=1,10-phenanthroline, PTA=terephthalic acid, p-MBA=p-toluic acid) has been determined by single-crystal X-ray diffraction. The crystal (C₄₈H₄₀CuN₄O₁₀, M_r=896.38) belongs to the monoclinic space group C2/c, with the following crystallographic parameters: a=1.778 6(3) nm, b=1.912 5(3) nm, c=1.389 9(2) nm, β=114.686(2)°, V=4.295 7(12) nm³, D_c=1.386 g·cm^-3, Z=4, μ(Mo Kα)=0.574 mm^-1, F(000)=1 860, final GooF=1.019, R=0.054 0, wR=0.148 3 for 2 644 observed reflections (I>2σ(I)). The crystal structure shows that the copper(Ⅱ) ion is coordinated with two oxygen atoms from one terephthalic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 298809.     

草酸根桥联Cr(Ⅲ)-Ni(Ⅱ)配合物的合成和磁性

Two new heteropolynuclear metal complexes ［Ni(phen)₂］₃［Cr(ox)₃］₂·8H₂O(1) and ［Ni(bipy)₂］₂［Cr(ox)₃］NO₃·4H₂O(2)(phen=1,10-phenanthroline, ox=oxalato, bipy=2,2-bipyridine) have been synthesized and characterized by elemental analyses, IR, TG-DTA and diffuse reflectance UV-VIS spectra. The temperature dependence of the magnetic susceptibilities of the complexes have been studied over the range 73.6～300K. The results show that ferromagnetic spin exchange interaction exist between Cr(Ⅲ) and Ni(Ⅱ) in the complex (1). The magnetic property of the complex(2) abides Curie law.     

草酸根桥联的双核铜(Ⅱ)配合物[Cu2(phen)2(H2O)2(μ2-C2O4)](NO3)2的合成及晶体结构

A new binuclear copper(Ⅱ) complex, [Cu₂(phen)₂(H₂O)₂(μ₂-C₂O₄)](NO₃)₂, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P2₁/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm³, D_c=1.769 Mg·m^-3, Z=2, F(000)=744, R₁=0.025 4, wR₂=0.069 5, Gof=1.077, Δρ=328～-455 e·nm^-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO₃^- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO₃^- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.