A Trinuclear Ni(Ⅱ) Mixed-ligand Complex Containing Pentadentate N-butylsalicylhydrazide and Monodentate Imidazole:Synthesis, Characterization and Crystal Structure

A novel trinuclear nickel(Ⅱ) complex [Ni3(bushz)2(Himdz)2(H2O)2]?2DMF (1, bushz=N-butylsalicylhydrazide, Himdz=imidazole, DMF=N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P21/c with a=7.706(7), b=14.882(6), c=18.639(6) , β=108.08(2)o, V=2032(1) 3, Dc=1.525 g/cm3, Mr=932.95, Z=2, F(000)=972, μ=1.442 mm-1, the final R=0.0359 and wR=0.0771. The three nickel(Ⅱ) atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3+/Ni2+ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.     

两个N-己酰基水杨酰肼合镍(Ⅱ)配合物的合成、结构及抗菌活性的研究

The two trinuclear nickel（Ⅱ） complexes, Ni3（C13H15N2O3）2（C5H5N）4 （1） and Ni3（C13H15N2O3）2（C5H5N）2- （C3H7NO）2 （2）, were prepared by the reaction of Ni（OAc）2·4H2O with N-hexanoylsalicylhydrazide. The crystal structures of complexes were determined by X-ray diffraction analysis. Complex 1 takes triclinic symmetry with space group P-1 and cell dimensions of a=0.92377（2） nm, b= 1.08786（6） nm, c= 1.29391（3） nm, α=76.395（4）°, β=78.418（3）°, γ=67.378（4）°, V= 1.15772（7） nm^3, Z= 1,μ= 12.63 cm^-1. Complex 2 belongs to triclinic system and P2（1） space group and the crystallographic data： a= 1.4889（2） nm, b= 1.0389（1） nm, c= 1.4994（2） nm, β= 96.174（4）°, V=2.3058（5） nm^3, Z=2,μ= 12.70 cm^-1. The structures of the two molecules are similar. The three nickel atoms in each molecule of the two title complexes arrange in a strictly linear structure. The central nickel atom of the molecule adopts octahedral configuration, while the two nickel atoms on the two sides adopt square-planar configuration in each molecule. But the central nickel atoms of the two complexes have different axial ligands, which cause a slight difference in the bond distances of the octahedron. The antibacterial activity of compound 1 against seven common bacteria was investigated.     

Simple Preparation,Structure and Conductivity of Nickel(Ⅱ) Benzenetricarboxylate Ni_3(BTC)_2·12H_2O

Proton-conductive crystalline metal-organic framework nickel(Ⅱ) benzenetricarboxylate Ni3(BTC)2·12H2O(MOF-Ni) was prepared by the reaction of nickel(Ⅱ) nitrate and 1,3,5-benzenetricarboxylic(BTC) acid in a mixed solvent of N,N-dimethylformamide(DMF)/C2H5OH/ H2O(1:1:1, ν/ν) at low temperature and short reaction time. It was characterized by thermogravimetric analyses(TG), FT-IR and N2 adsorption-desorption. Single-crystal X-ray diffraction analysis indicated that the complex belongs to monoclinic system, space group C2 with a = 17.407(6), b = 12.878(5), c = 6.542(2) , β = 112.07°, V = 1359.0(8)3, Dc = 1.971 g/cm3, μ = 2.166 mm-1 and Z = 2. Linear polarization resistance(LPR) analysis showed that the complex possesses semiconducting properties.     

Synthesis and Crystal Structure of Diaquabis{2,4-dibromo-6-[(2-ethylaminoethylimino)methyl]-phenolato}nickel(Ⅱ) Dinitrate Diacetonitrile

The title mononuclear Schiff base nickel(Ⅱ) complex [Ni(C11H14Br2N2O)2(H2O)2]· 2NO3·2C2H3N was prepared and characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group P21/n with a=15.534(2),b=7.647(1),c=16.435(2),β=103.252(2)o,V=1900.3(4)3,Z=2,Dc=1.750 g/cm3,Mr=1000.99,λ(MoKα)=0.71073,μ=4.776 mm-1,F(000)=996,the final R=0.0368 and wR=0.0724. A total of 3988 unique reflections were collected,of which 2764 with I > 2σ(I) were observed. The complex consists of a mononuclear [Ni(C11H14Br2N2O)2(H2O)2]2+ cation,two nitrate anions and two acetonitrile molecules. The Ni atom,lying on the inversion centre,is six-coordinated by two Schiff bases and two water molecules to assume an octahedral coordination geometry. The molecules in the crystal are linked through intermolecular hydrogen bonds of N–H…O,N–H…Br,O–H…O,O–H…N and C–H…O to form layers.     

Crystal Structure,Spectroscopic Characterization,and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel(Ⅱ) complex Ni_2(L)_2(2,2?-bipy)2·5.5H_2 O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid(H2L) and 2,2?-bipyridine(2,2?-bipy) as ligands has been synthesized in the mixed solvent DMF and water(v:v = 5:2). It crystallizes in the triclinic space group P1 with a = 10.414(2), b = 12.884(3), c = 16.176(4) ?, α = 70.715(5), β = 80.599(5), γ = 77.383(6)o, V = 1989.4(8) ?3, Dc = 1.531 g/cm3, Z = 2, F(000) = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1:η0 3-carboxylate groups of L2- anions. The coordination environment of Ni(Ⅱ) ion is Ni N_2O_3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.     

A New Three-dimensional Supramolecular Polymer Built from Non-covalent Bonding Interactions

A new complex, [Ni2(L)4(H2O)8](1, L1 = 4-(1H-imidazol-4-yl)benzoic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 22.281(2), b = 7.3959(7), c = 24.978(3) ?, β = 90.876(10), V = 4115.6(7) ?3, Z = 8, C20H22N4O8Ni, Mr = 505.13, Dc = 1.630 g/cm3, μ = 1.001 mm-1, S = 1.080, F(000) = 2096, the final R = 0.452 and wR = 0.1152 for 9380 observed reflections(I 2σ(I)). The result of X-ray diffraction analysis revealed three different kinds of Ni(II) centre mononuclear molecules in the asymmetric unit. The independent mononuclear units are bridged to form a three-dimensional supramolecular polymer by extensive hydrogen bonds and C–H···π non-covalent bonding interactions.     

Syntheses and Crystal Structures of Cd(Ⅱ) and Ni(Ⅱ) Complexes Containing Flexible Sulfide and Nitrogen Heterocyclic Ligands

Two new coordination polymers [Cd(EBLA)(ip)(H2O)](1) and [Ni(EBSA)(im)2(H2O)]n(2) were synthesized by hydrothermal and solution methods using 2,2'-dithiosalicylicacid(EBSA), 1H-imidazo[4,5-f][1,10]phenanthroline(ip), imidazole(im), Cd(NO3)2·4H2O and Ni(NO3)2·6H2O. The complexes were characterized by elemental analysis and FT-IR. Meanwhile, the crystal structures, fluorescence properties of complex 1 and thermogravimetrie analysis of complex 2 have been studied. In complex 1, 2,2'-dicarboxydiphenylthioether(EBLA) was prepared with 2,2'-dithiosalicylicacid(EBSA) in situ reaction by hydrothermal method. Complex 1 is a dinuclear structure and Cd2+ is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 is a one-dimensional infinite linear chain and Ni2+ is six-coordinated to form a distorted octahedral geometry. Hydrogen bonding and π-π interactions are observed in these complexes.     

Synthesis,Crystal Structure and Fluorescence Property of a New Trinuclear Nickel(Ⅱ) Complex Bridged by 2,6-Pyridine Dicarboxylic Acid

A new trinuclear nickel complex,[Ni3(pdc)3(2,2'-bipy)3(H2O)2]·2H2O(H2pdc = pyridine 2,6-dicarboxylic acid,2,2'-bipy = 2,2'-bipyridine) has been hydrothermally synthesized and characterized by IR,elemental analysis and X-ray diffraction methods.Crystal data for this complex:monoclinic,space group P21/n,a = 21.206(4),b = 10.002(2),c = 28.066(6),β = 108.18(3)°,C51H41N9Ni3O16,Mr = 1212.06,V = 5.656(2) nm3,Dc = 1.423 g·cm-3,μ(MoKα) = 1.062 mm-1,Z = 4,F(000) = 2488,GOOF = 1.034,the final R = 0.0543 and wR = 0.1237 for 6149 observed reflections with Ⅰ 2σ(Ⅰ).In the complex,three nickel(Ⅱ) ions are bridged by the pyridine 2,6-dicarboxylic acid groups,and all nickel(Ⅱ) ions are seven-coordinated by nitrogen atoms of 2,2'-bipyridine and pyridine 2,6-dicarboxylic acid and oxygen atoms from pyridine 2,6-dicarboxylic and water to adopt a severely distorted pentagonal bipyramidal geometry.The emission and excitation peaks of the complex in ethanol solutions are located at 336 and 316 nm,respectively.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex Based on a Carboxyl-substituted 1H-1,2,3-Triazole and Its DNA Cleavage Activity

The novel dinuclear copper complex [Cu2(H2O)2(DMF)2(L)2](1, H2 L = 5-phenyl-2H-1,2,3-triazole-4-carboxylic acid, DMF = N,N-dimethyl-formamide) has been synthesized and characterized by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1 with a = 9.591, b = 10.508, c = 15.515 ?, β = 75.11°, V = 1446.2 ?3, Z = 2, Mr = 683.62, Dc = 1.570 g/cm3, μ = 1.531 mm-1, F(000) = 700, the final R = 0.0404 and w R = 0.1130 for 5327 observed reflections with I 2σ(I). In each unit of the complex, two Cu2+ ions coordinated with two triazole ligands to form a dimeric [5,6,5] tricyclic structure. The central Cu atom is five-coordinated, and each copper atom shows a square pyramidal geometry. The crystal structure is stabilized by the inversion-related O–H···O hydrogen bond and C–H···O hydrogen bonding interactions to form a layer structure. Fluorescent spectra show an obvious quenching of fluorescence compared with free 1,2,3-triazole ligand. The results of agarose gel electrophoresis indicate that this complex can cleave the plasmid supercoiled DNA within shorter time in the 50-folds excess of ascorbate under physiological conditions, providing a new example in the research for artificial metal nucleic acid enzyme.     

Synthesis, Characterization, Crystal Structure and Antibacterial Activities of a Nickel(Ⅱ) Complex with 2'-(2-Thienylidene)-hydroxybenzoylhydrazide

In the ethanol solvent, a nickel(II) complex Ni(C12H10N2O2S)2 upon reaction of 2'-(2-thienylidene)-hydroxybenzoylhydrazide with nickel acetate was synthesized, and its structure was characterized by IR, UV, elemental analysis and X-ray diffraction analysis. The crystal belongs to monoclinic system, space group C2/c with a = 22.052(3), b = 5.9681(6), c = 18.522(2) , β = 110.679(4)°, V = 2280.6(4) 3, Z = 4, Mr = 551.27, μ = 1.606 mm-1, Dc = 1.075 g/cm3, F(000) = 1136 and Rint = 0.0556. The nickel(Ⅱ ) atom in the compound is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The biological activities have been measured, show- ing the compound exhibits better anti-bacterial activity than the ligand.     

Structural and magnetic studies of Schiff base complexes of nickel(II) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO' bridging mode

Four new nickel(II) complexes, [Ni(2)L(2)(NO(2))(2)]·CH(2)Cl(2)·C(2)H(5)OH, 2H(2)O (1), [Ni(2)L(2)(DMF)(2)(μ-NO(2))]ClO(4)·DMF (2a), [Ni(2)L(2)(DMF)(2)(μ-NO(2))]ClO(4) (2b) and [Ni(3)L'(2)(μ(3)-NO(2))(2)(CH(2)Cl(2))](n)·1.5H(2)O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H(2)L(') = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL(2)]·2H(2)O, nickel(ii) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, Ni(II) ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-μ(2)-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(μ-nitrito-1κO:2κN) bridge is present in addition to the di-μ(2)-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as μ-nitrito-1κO:2κN bridged trinuclear units are linked through a very rare μ(3)-nitrito-1κO:2κN:3κO' bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(ii) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm(-1) for 1, 2a, 2b and 3, respectively.     

An unsymmetrical tripodal ligand with an N2OS donor set: coordination chemistry with nickel(II)ions and aerial oxidation to the sulfinate complex

The synthesis of the previously unknown tripodal ligand H4-1 is reported. The tetradentate ligand is equipped with a completely unsymmetrical N2OS donor set. It reacts with Ni(OAc)2. 4H2O or Ni(ClO4)2.6H2O to give the multinuclear nickel(II) complexes [Ni(H-1-Imin)(OAc)]2 (2) (which contains a coordinated Schiff base obtained by reation of the primary amine with the acetone solvent) and [Ni3(H3-1)(H2-1)2]-ClO4.H2O.3 MeCN (3), respectively. A solution of 3 in DMF is readily oxidized upon exposure to air or by aqueous H2O2 to yield [Ni(H2-1-sulfinate)]2. 2MeOH (4). The molecular structures of 2-4 have been determined by X-ray diffraction. Complex 2 exhibits a strongly distorted, octahedral coordination geometry around each nickel(II)ion. The primary amino group of the ligand in this case reacted with the solvent acetone to yield a Schiff base which is coordinated to the metal center. The molecular structure of the trinuclear complex cation in 3 consists of two subunits: a nickel atom with a square-planar N2S2 coordination geometry and two other nickel atoms with a trigonal-bipyramidal N2O2S coordination environment. The dinuclear complex 4 shows distorted octahedral geometry around each nickel(II) ion. The thiolato groups of the ligands are oxidized to sulfinato groups which are O,O-bound to the nickel center. This coordination mode is unusual for nickel sulfinate complexes.     

Pendant macrocyclic metallic building blocks for the design of cyano-bridged heterometallic complexes with 1D chain and 2D layer structures

A series of cyano-bridged Ni(II)-Cr(I/III) complexes have been synthesized by the reactions of hexaazacyclic Ni(II) complexes with [Cr(CN)(6)](3-) or [Cr(CN)(5)(NO)](3-). Using the tetravalent Ni(II) complex [Ni(H(2)L(2))](4+) (L(2) = 3,10-bis(2-aminoethyl)-1,3,6,8,10,12-hexaazacyclotetradecane), one-dimensional chainlike complexes were produced and subject to magnetic studies, affording the intermetallic magnetic exchange constants of J(1) = +0.23 cm(-1) and J(2) = +8.4 cm(-1) for the complex [Ni(H(2)L(2))][Cr(CN)(5)(NO)]ClO(4).5H(2)O (1) and of J = +5.9 cm(-1) for the complex [Ni(H(2)L(2))](4)[Cr(CN)(6)](5)OH.15H(2)O (2). X-ray diffraction analysis shows that complex 1 has a zigzag chain structure, whereas complex 2 consists of a branched chain structure. Complex 2 exhibits antiferromagnetic ordering at 8.0 K (T(N)). When an octahedral Ni(II) complex cis-[NiL(3)(en)](2+) (en = 1,2-ethylenediamine, L(3) = 3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) was used for the synthesis, the common 2D honeycomb-layered complex [NiL(3)](3)[Cr(CN)(5)(NO)](2).8H(2)O (3) was obtained, which has a T(N) value of 3.3 K. Below T(N), a metamagnetic behavior was observed in complexes 2 and 3.     

Macrocyclic nickel(II) complexes coligated by hydrosulfide and hexasulfide ions: syntheses, structures, and magnetic properties of [NiII2L(mu-SH)]+ and [(LNiII2)2(mu-S6)]2+

The borohydride complex [Ni(II)2L(mu-BH4)]+ (3) where L(2-) represents a sterically demanding hexaaza-dithiophenolate ligand reacts rapidly with elemental sulfur in acetonitrile at ambient temperature to produce the cationic complexes [Ni(II)2L(mu-SH)]+ (4) and [(Ni(II)2L) 2(mu-S6)]2+ (6). Both complexes were isolated as ClO4(-) or BPh4(-) salts and characterized by IR and UV/vis spectroscopy and X-ray crystallography. Complex 4 (also accessible from [Ni(II)2L(ClO4)]+ (5) and Na2S.9H2O) features an unprecedented N3Ni(II)(mu-SR)2(mu-SH)Ni(II)N3 core structure, the hydrosulfide ligand being deeply buried in the binding-cavity of the bowl-shaped [Ni(II)2L]2+ complex. In 6, a helical S6(2-) chain, with a structure reminiscent to that of plastic sulfur, is almost completely encapsulated by two [Ni(II)2L]2+ subunits. In contrast to other triply sulfur-bridged N3Ni(II)(SR)3Ni(II)N3 structures whose ground states are typically of S = 0, 4 reveals an S = 2 ground-state which is attained by a ferromagnetic exchange interaction between the two Ni(II) (S = 1) ions ( J = 18 cm (-1), H = -2JS1S2). Intradimer ferromagnetic exchange interactions are also present in 6 ( J = 23 cm (-1)). A qualitative explanation for this difference is offered.     

Synthesis and Structure of Nickel(II) Compound with Tetradentate Schiff-base Ligand and Diazido Monohydrate

1 INTRODUCTION Complexes of ligands which bind two or more metal centers in close proximity are important as potential catalysts[1], as models for a number of metalloproteins[2], and because of the opportunity they provide for the investigation of magnetic interactions. The structural and magnetic properties of binuclear and polymetallic nickel (II) complexes with various bridging ligands have received considerable attention in the past three decades[3～6]. At present, there is a spectacu…     

Anion-controlled nuclearity in nickel complexes with potentially dinucleating, poly(oxime) amine ligands

Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. [Ni(2)(L2)Cl(4)(DMF)](2).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8.     

Kinetics and mechanism of complex formation of nickel(II) with tetra-N-alkylated cyclam in N,N-dimethylformamide (DMF): comparative study on the reactivity and solvent exchange of the species Ni(DMF)6(2+) and Ni(DMF)5Cl+

13C NMR was used to study the rate of DMF exchange in the nickel(II) cation Ni(DMF)6(2+) and in the monochloro species Ni(DMF)5Cl+ with 13C-labeled DMF in the temperature range of 193-395 K in DMF (DMF = N,N-dimethylformamide). The kinetic parameters for solvent exchange are kex = (3.7 +/- 0.4) x 10(3) s-1, delta H++ = 59.3 +/- 5 kJ mol-1, and delta S++ = +22.3 +/- 14 J mol-1 K-1 for Ni(DMF)6(2+) and kex = (5.3 +/- 1) x 10(5) s-1, delta H++ = 42.4 +/- 4 kJ mol-1, and delta S++ = +6.7 +/- 15 J mol-1 K-1 for Ni(DMF)5Cl+. Multiwavelength stopped-flow spectrophotometry was used to study the kinetics of complex formation of the cation Ni(DMF)6(2+) and of the 100-fold more labile cation Ni(DMF)5Cl+ with TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and TEC (1,4,8,11-tetraethyl-1,4,8,11-tetraazacyclotetradecane) in DMF at 298 K and I = 0.6 M (tetra-n-butylammoniumperchlorate). Equilibrium constants K for the addition of the nucleophiles DMF, Cl-, and Br- to the complexes Ni(TMC)2+ and Ni(TEC)2+ were determined by spectrophotometric titration. Formation of the complexes Ni(TMC)2+ and Ni(TEC)2+ was found to occur in two stages. In the initial stage, fast, second-order nickel incorporation with rate constants k1(TMC) = 99 +/- 5 M-1 s-1 and k1 (TEC) = 235 +/- 12 M-1 s-1 leads to the intermediates Ni(TMC)int2+ and Ni(TEC)int2+, which have N4-coordinated nickel. In the second stage, these intermediates rearrange slowly to form the stereochemically most stable configuration. First-order rate constants for the one-step rearrangement of Ni(TMC)int2+ and the two-step rearrangment of Ni(TEC)int2+ are presented. Because of the rapid formation of Ni(DMF)5Cl+, the reactions of Ni(DMF)6(2+) with TMC and TEC are accelerated upon the addition of tetra-n-butylammoniumchloride (TBACl) and lead to the complexes Ni(TMC)Cl+ and Ni(TEC)Cl+, respectively. For initial concentrations such that [TBACl]o/[nickel]o > or = 20, intermediate formation is 230 times (TMC) and 47 times (TEC) faster than in the absence of chloride. The mechanism of complex formation is discussed.     

基于香豆素Schiff碱双核Ni（Ⅱ）和立方烷型Cu4（μ3-O）4的四核Cu（Ⅱ）配合物的合成、晶体结构及光谱性质（英文）

合成了2个3-氨基-4-羟基香豆素类Schiff碱双核Ni?髤和立方烷型Cu4(μ3-O)4的四核Cu?髤配合物,[Ni(L1)(DMF)(H2O)]2(1)(H2L1=3-((5-溴-2-羟基-亚苄基)-氨基)-4-羟基-苯并吡喃-2-酮)和[Cu4(L2)4]·DMF·CH3OH·2H2O(2)(H2L2=4-羟基-3-((2-羟基-3-甲氧基-亚苄基)-氨基)-苯并吡喃-2-酮),并通过元素分析、红外光谱、紫外光谱、荧光光谱及X射线单晶衍射分析等手段进行了表征。X射线单晶衍射分析结果表明:配合物1具有双核结构,由2个金属离子和2个配体单元组成,配合物2具有立方烷型Cu4(μ3-O)4的四核结构,由4个金属离子和4个配体单元组成。配合物1是单斜晶系、C2/c空间群;配合物2是四方晶系,I41/a空间群,且中心金属Ni?髤和Cu?髤离子的空间构型均为六配位的扭曲的八面体。此外,配合物1通过分子间氢键、C-H…π及π…π作用形成1D超分子链结构,配合物2通过分子内氢键和π…π作用形成3D超分子结构。此外,研究了H2L1,H2L2及其相应的Ni?髤和Cu?髤配合物的荧光性质。     

Syntheses, structures, and magnetic properties of a family of tetra-, hexa-, and nonanuclear Mn/Ni heterometallic clusters

A family of Mn(III)/Ni(II) heterometallic clusters, [Mn(III)(4)Ni(II)(5)(OH)(4)(hmcH)(4)(pao)(8)Cl(2)]·5DMF (1·5DMF), [Mn(III)(3)Ni(II)(6)(N(3))(2)(pao)(10)(hmcH)(2)(OH)(4)]Br·2MeOH·9H(2)O (2·2MeOH·9H(2)O), [Mn(III)Ni(II)(5)(N(3))(4)(pao)(6)(paoH)(2)(OH)(2)](ClO(4))·MeOH·3H(2)O (3·MeOH·3H(2)O), and [Mn(III)(2)Ni(II)(2)(hmcH)(2)(pao)(4)(OMe)(2)(MeOH)(2)]·2H(2)O·6MeOH (4·2H(2)O·6MeOH) [paoH = pyridine-2-aldoxime, hmcH(3) = 2, 6-Bis(hydroxymethyl)-p-cresol], has been prepared by reactions of Mn(II) salts with [Ni(paoH)(2)Cl(2)], hmcH(3), and NEt(3) in the presence or absence of NaN(3) and characterized. Complex 1 has a Mn(III)(4)Ni(II)(5) topology which can be described as two corner-sharing [Mn(2)Ni(2)O(2)] butterfly units bridged to an outer Mn atom and a Ni atom through alkoxide groups. Complex 2 has a Mn(III)(3)Ni(II)(6) topology that is similar to that of 1 but with two corner-sharing [Mn(2)Ni(2)O(2)] units of 1 replaced with [Mn(3)NiO(2)] and [MnNi(3)O(2)] units as well as the outer Mn atom of 1 substituted by a Ni atom. 1 and 2 represent the largest 3d heterometal/oxime clusters and the biggest Mn(III)Ni(II) clusters discovered to date. Complex 3 possesses a [MnNi(5)(μ-N(3))(2)(μ-OH)(2)](9+) core, whose topology is observed for the first time in a discrete molecule. Careful examination of the structures of 1-3 indicates that the Mn/Ni ratios of the complexes are likely associated with the presence of the different coligands hmcH(2-) and/or N(3)(-). Complex 4 has a Mn(III)(2)Ni(II)(2) defective double-cubane topology. Variable-temperature, solid-state dc and ac magnetization studies were carried out on complexes 1-4. Fitting of the obtained M/(Nμ(B)) vs H/T data gave S = 5, g = 1.94, and D = -0.38 cm(-1) for 1 and S = 3, g = 2.05, and D = -0.86 cm(-1) for 3. The ground state for 2 was determined from ac data, which indicated an S = 5 ground state. For 4, the pairwise exchange interactions were determined by fitting the susceptibility data vs T based on a 3-J model. Complex 1 exhibits out-of-phase ac susceptibility signals, indicating it may be a SMM.     

含硫镍金属镍配合物[Ni(C13H7Br2NOS)2(DMF)]·(C3H7O)的合成与晶体结构

The complex, Ni[(C₁₃H₇Br₂NOS)₂(DMF)]·(C₃H₇O) (DMF=N,N′-dimethylformamide), was synthesized and characterized by the element analysis, IR and X-ray diffraction single crystal structure determination. The title complex crystallizes in monoclinic system, space group P2₁/n, with a=8.297 6(15) nm, b=12.866(2) nm, c=31.889(3) nm, β=95.024(2)°, and V=3 391.3(9) nm³, Z=4, R=0.075 2, wR=0.176 8. The nickel iron is six-coordinated by three O atoms, two N atoms, one S from the Schiff base and one O atom from DMF ligand, forming a octahedron coordination geometry. Schiff bases are bridged by the two S atoms. The molecules in the crystal are linked through intermolecular Br…Br, C-H…O, S…Br interactions. Its electrochemical property is reported. CCDC: 675768.