Molecular structure of imidazolate bridged binuclear zinc complex and its single crystal ESR spectra doped with bridged Cu—Zn complex

The X-ray crystal structure of [(dtma)ZnImZn(dtma)]ClO_4·2.5H_2O (Hdtma=4-Diethyl-enetriamineacetic acid) was determined.The crystal is of orthorhombic,space group Pbcn with a-14.104(5),b=14.897(5),c=25.384(9),and Z=8.The least-square refinement of the structureleads to conventional R factor of 0.066.The magnetic properties of [(dtma)CulmZn(dtma)]CIO_4·2.5H_2Owere investigated.From the single crystal ESR spectra of Zn—Im—Zn dimer doped withCu—Im—Zn complex,the anisotropic g and A tensors and electronic spin-density of the Cu—Zncomplex are obtained and the bonding nature of Cu is discussed.     

Synthesis,crystal structure and magnetic properties of a new macrocyclic binuclear copper(II) complex

A new binuclear copper complex [CuLCl₂]₂, [L = 1-(p-tolylsulfonyl)-1,4,7- triazacyclononane], has been synthesized and structured as well as magnetically characterized. In the complex, each copper(II) atom is located in the center of a distorted square pyramidal configuration of five coordinating atoms (two nitrogen atom and three chlorine atom). Two copper(II) atoms were bridged by two chlorine anions (Cl1 and Cl1a). The distance between two copper(II) atoms is 3.483 Å. An antiferromagnetic exchange coupling effect exists in the complex.     

2-氨基对苯二甲酸双核铜配合物的合成与晶体结构

合成了一种新的铜配合物[Cu2(μ-2-atp)(phen)4].2ClO4(2-atp为2-氨基对苯二甲酸,phen为邻菲咯啉),利用红外光谱和X射线单晶衍射表征了产物的结构,利用元素分析测定了其元素组成,利用热重分析考察了其热分解行为.结果表明,标题化合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.971 0(9)nm,b=1.187 8(1)nm,c=1.234 9(1)nm,α=70.104 0(1)°,β=68.699 0(1)°,γ=86.719 0(1)°,V=1.244 1(2)nm3,Z=1,Dc=1.635g/cm3,μ=1.041mm-1,F(000)=623,R1=0.058 4,wR2=0.129 3.该化合物具有双核铜结构,通过强烈的π-π堆积作用形成二维超分子结构.     

Synthesis and crystal structure of a new copper(II) binuclear complex bridged by the reduced derivative of a nitronyl nitroxide biradical

A new copper(II) binuclear complex, [Cu(hfac)₂]₂(IMH)₂Ph(OMe)₂ ((IMH)₂Ph(OMe)₂?=?2,5-dimethoxyl-1,4-bis(4′,4′,5′,5′-tetramethylimidazoline-3′-oxide)benzene, hfac?=?hexafluoroacetonate), bridged by a reduced derivative of a nitronyl nitroxide biradical has been synthesized and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group P2₁/n, with a?=?10.002(14), b?=?19.950(3), c?= 14.504(2) Å, β?=?108.842(3)° and Z?=?2. The structure refined to a final R value of 0.0644. The complex contains two copper(II) ions bridged by a reduced derivative of a nitronyl nitroxide biradical with a Cu?···?Cu separation of 8.430(2) Å.     

Synthesis,spectral and ferromagnetic interactions in isophthalato bridged binuclear copper(II) complexes

Transition Metal Chemistry - Four novel copper(II) binuclear complexes have been synthesized and characterized, namely [Cu2(IPHTA)( L)2](ClO4)2 (L denotes 2,2′-bipyridine (bpy); 1,10-...     

酰腙席夫碱铜单核配合物的合成、结构及性质

合成了一个铜单核配合物Cu(HL)2(H2L=(水杨酸乙酯缩水合肼)缩2-吡啶甲醛),利用红外光谱,紫外-可见光谱和X射线单晶衍射对这个配合物的结构和性质进行了表征.结果表明,该配合物属正交晶系,Aba2空间群,晶胞参数为a=1.292 0(2)nm,b=1.806 0(3)nm,c=1.092 4(2)nm,α=β=γ=90°,V=2.549 0(7)nm3,Z=4,Dc=1.418g·cm-3,μ=0.901 mm-1,F(000)=1 116,R1=0.074 9,wR2=0.164 9.配合物的结构是两个配体夹着一个金属铜原子的十字交叉结构.     

Synthesis,structure and properties of complex compounds of cobalt,nickel, copper and zinc with 2-formylpyridine semicarbazone

2-Formylpyridine semicarbazone L reacts with cobalt, nickel, copper and zinc chlorides, nitrates and perchlorites to form coordination compounds of compositions ML₂X₂·nH₂O (M=Co, Ni, Cu, Zn; X = Cl, NO₃, ClO₄; L = NC₅H₄-CH=N-NH-C(O)-NH₂; n = 0, 1) and CuLX₂·nH₂O (X = Cl, Br, NO₃; n = 0−0.5). Complex CuL(NO₃)₂ has polynuclear, CuLX₂·0.5H₂O (X = Cl, Br), binuclear, and other compounds, mononuclear structures. Azomethine L behaves in them as tridental N,N,O-ligand. Thermolysis of these complexes proceeds through such stages as dehydration (80–95°C), deactivation (145–155°C) and complete theral degradation (170–590°C). Complexes CuLX₂·nH₂O (X = Cl, NO₃; n = 0−0.5) were established to inhibit in vitro the growth and reproduction of 100% of cancer cells of human mieloid leukaemia HL-60 at 10⁻⁴ M concentration. At 10⁻⁵ M concentration they inhibit only 10% of cells, and at 10⁻⁶ M concentration they do not possess anticancer activity.     

Synthesis,crystal structure,and DNA binding of a new oxalato-bridged binuclear zinc(II) complex

A new binuclear zinc(II) complex bridged by μ-oxalate, and end-capped with 2,2′-bipyridine (bpy), [Zn₂(ox)(bpy)₄](ClO₄)₂ · H₂O, has been synthesized and characterized by elemental analyses, molar conductance, IR, and electronic spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the [Zn₂(ox)(bpy)₄]²⁺ cation has two zinc(II) centers bridged by a planar bis(bidentate) oxalate group with Zn···Zn distance of 5.482(3) Å; each zinc(II) is in a distorted octahedral environment. The crystal structure is stabilized by non-classical C–H···O hydrogen bonds and π–π stacking interactions to form a 3-D supramolecular structure. The interaction of the complex with calf-thymus DNA (CT-DNA) was explored by using electronic and fluorescence spectra and viscosity measurements. The results reveal that the complex intercalates with CT-DNA with intrinsic binding constant of 4.1 × 10⁴ M^?1.     

Synthesis, crystal structure, and luminescent properties of a binuclear gallium complex with mixed ligands

By introducing tridentate Schiff base ligands, a binuclear gallium complex with mixed ligands, bis(salicylidene-o-aminophenolato)-bis(8-quinolinolato)-bis-gallium(III) [Ga(2)(saph)(2)q(2)], has been synthesized and structurally characterized by single-crystal X-ray crystallography. Crystal data for C(44)H(30)Ga(2)N(4)O(6) are as follows: space group, triclinic, P; a = 11.357(3) A, b = 12.945(3) A, c = 12.947(3) A, alpha = 103.461(15) degrees, beta = 100.070(7) degrees, gamma = 96.107(18) degrees, Z = 2. This complex was identified as a dimeric complex of hexacoordinated gallium with strong intermolecular and intramolecular pi-pi stacking interactions between the pyridyl/pyridyl rings. The thermal analysis showed that Ga(2)(saph)(2)q(2) can readily form a stable amorphous glass with a high glass transition temperature (T(g) = 204 degrees C), which is 27 degrees C higher than that of tris(8-hydroxyquinolinolate)aluminum (Alq(3)). In addition, a high photoluminescence efficiency (phi(PL)) of 0.318 in DMF has been demonstrated, although the central gallium atom can result in heavy-atom quenching. Organic light-emitting diodes (OLEDs) based on this complex displayed a turn-on voltage as low as 2.5 V and a high efficiency. Even at a low doping concentration of 1%, the doped Ga(2)(saph)(2)q(2) devices with 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as the dopant exhibited excellent red emission centered at 628 nm with improved durability, compared with the case of Alq(3) as the host. These distinguishing properties of Ga(2)(saph)(2)q(2) make it a good candidate as a novel electron-transporting and emitting material for OLEDs.     

Synthesis,crystal structure,and magnetism of a binuclear Cu(II) complex with a single end-to-end bridged azido ligand

A binuclear copper(II) complex, [Cu₂(μ _1,3-N₃)(N₃)(pmp)₂(ClO₄)]ClO₄ (pmp = 2-((pyridin-2-yl) methoxy)-1,10-phenanthroline), was synthesized with a single azide as end-to-end bridge ligand, and pmp and perchlorate as ligands. In the crystal, Cu(II) is in a distorted square pyramidal geometry, and a single azide bridges equatorial-axial linking two Cu(II) ions with separation of 5.851 Å. There are π?π stacking interactions involving 1,10-phenanthroline rings. The variable-temperature (2–300 K) magnetic susceptibilities were analyzed using a binuclear Cu(II) magnetic formula and it indicates that there is a very weak ferromagnetic coupling with 2J = 2.82 cm^?1.     

Synthesis, structure and characterization of binuclear copper(Ⅱ) complexes

At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.     

Synthesis,structure and characterization of binuclear copper(I) complexes

Binuclear copper(I) complexes [Cu(dppm)(NO3)]2 (1), dppm=Ph2PCH2PPh2, [Cu(dppm)(2,9-Me2Phen)]2(NO3)2 (2), [Cu(dppm)(I)]2 (3) and [Cu(dppm)(py)]2(NO3)2 (4), (py=pyridine) have been synthesized by ligand reduction of cupric nitrate with dppm in EtOH and characterized by elemental analyses, molecular weight determination, t.g.a., 31P-n.m.r spectra; their electronic conductivities and c.v. waves have also been measured. The results show that dppm coordinates as a bridging bidentate ligand to the CuI atoms, and that NO3 behaves as a monodentate ligand or free ion in the newly prepared complexes.     

Synthesis,crystal structure and properties of a 1D copper(II) complex with 1,5,9-triazacyclododecane bridged by p -benzenebicarboxylate

A 1D complex [{[Cu₂([12]aneN₃)₂(p-paa)(H₂O)₂](ClO₄)₂}[Cu₂([12]aneN₃)₂(p-paa)₂]] _n ([12]aneN₃ = 1,5,9-triazacyclododecane, p-paa = p-benzenebicarboxylate) has been synthesized and structurally characterized. The complex contains two different binuclear copper(II) moieties. One part includes a binuclear copper(II) unit and non-coordinated perchlorate anions. A neutral binuclear copper(II) part which forms a zigzag chain structure via the bridging p-paa ligand completes the unit-cell. Elemental analysis, IR, UV-Vis spectra and magnetic properties for the complex have also been determined. Magnetic susceptibilities in the solid state are measured over the temperature range from 77 to 300 K, showing a weak antiferromagnetic coupling with a best fit J ₁ = ?3.09 cm^?1, J ₂ = ?5.279 cm^?1, g = 2.099 and R = 1.226 × 10^?5.     

Synthesis,crystal structure and properties of di-μ2-alkoxo bridged binuclear manganese(III) Schiff base complexes

Transition Metal Chemistry - Preparation and isolation of the dimeric manganese(III) complex, [Mn2(Salpa)2(H2O)2Cl2] · 2DMF, (1), was accomplished by air oxidation of a solution containing...     

Synthesis,spectral and magnetic properties of binuclear copper(II)/nickel(II) and copper(II) complexes bridged by glyoximate groups

Three new dinuclear complexes, [(tmen) (H2O)2Ni (Hdmg)(dmg)Cu]·ClO4, [(dien)(H2O)Ni (Hdmg)(dmg) Cu]·ClO4 and [(tmen)Cu(Hdmg)(dmg) Cu] ClO4·H2O (H2dmg=dimethylglyoxime, tmen=tetramethylene diamine), have been prepared. Variable-temperature- magnetic susceptibility measurements (75–300K) on the complexes reveal the presence of intramolecular antiferromagnetic interactions through the oximate bridges. The formation of mononuclear, dinuclear complexes has been confirmed by spectrophotometry.     

Synthesis,structure, anticancer activities,and DNA-binding properties of a 1-D polymeric copper(II) complex alternately bridged by oxamide and terephthalate

A 1-D polymeric copper(II) complex alternately bridged by N,N′-bis(N-hydroxyethylaminopropyl)oxamide (heap^2?) and terephthalate (tpa^2?), [Cu₂(heap)(tpa)] _n , has been synthesized and characterized by single-crystal X-ray diffraction. The crystal structure reveals that the asymmetric unit of the copper(II) polymer is half a dinuclear copper(II) complex, [Cu₂(heap)(tpa)], in which Cu(II) is located in a square-pyramidal coordination environment. Separations of Cu(II) through heap^2? and tpa^2? bridges are 5.2459(6) and 11.1375(6)?Å, respectively. The complex chains, accompanied with glide planes parallel to the a0c plane, can be classified to two groups according to their extending direction. Hydrogen bonds occur between a complex chain and any adjacent ones in the other orientation. Consequently, a 3-D supramolecular network is completed. The polymeric copper(II) complex exhibits potent anticancer activities against human hepatocellular carcinoma cell SMMC-7721 and human lung adenocarcinoma cell A549 tested by sulforhodamine B assays. The interactions of the polymeric copper(II) complex with herring sperm DNA (HS-DNA) are investigated by using electronic absorption titration, fluorescence titration, electrochemical titration, and viscometry measurements. The results suggest that the polymeric copper(II) complex interacts with HS-DNA via intercalation with intrinsic binding constant of 1.8?×?10^6?(mol?L^?1)^?1.     

Synthesis and magnetic properties of a new binuclear copper(II) complex with naphthalato-bridged ligand

To utilized a bridged-ligand of 1,8-naphthalate dianion (NAPH) as building block by self-assembly technology, a new binuclear copper(II) compound [Cu₂(μ-NAPH)₂(DMF)₄(H₂O)₂] (I) has been constructed and structurally characterized by X-ray crystallography. Complex I crystallizes in monoclinic, space group C2/c, with a = 17.822(9), b = 9.964(5), c = 23.194(11) Å and β = 102.385(5)°. Magnetic measurements confirm that I presents a very weak antiferromagnetic interaction between the paramagnetic ions.     

Synthesis,crystal structure and magnetic properties of a new binuclear copper(II)-copper(II) complex of a macrocyclic oxamide

The binuclear metal complex [Cu(μ-exoO₂)cyclamCu(bpy)](ClO₄)₂·H₂O (bpy?=?2,2′-bipyridine and (exoO₂)cyclam?=?1,4,8,11-tetraazacyclotradecanne-2,3-dione) has been synthesized and characterized by single-crystal X-ray analysis and spectroscopic and magnetic measurements. The structure consists of homobinuclear [Cu(μ-exoO₂)cyclamCu(bpy)]²⁺ cations, a weakly coordinated water molecule and perchlorate ions. In each binuclear unit, Cu1, coordinated by four nitrogen atoms of the macrocyclic organic ligand is connected to Cu2 via the exo-cis oxygen atoms of the macrocyclic ligand with Cu···Cu separations of 5.151?Å; Cu2 assumes square-pyramidal geometry. Magnetic properties measured at 2–300?K show antiferromagnetic exchange between adjacent copper(II) ions.