Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln(DMSO)_2(H_2O)(μ-CN)_4Fe(CN)_2] (Ln = Ce and Eu, DMSO = Dimethylsulfoxide) with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln（DMSO）2（H2O）（μ-CN）4Fe（CN）2] （Ln = Ce 1, Eu 2） have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1： C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852（4）, b = 10.729（5）, c = 11.181（5）A,β = 96.992（8）°, V = 935.0（7） A^3, Z = 2, Dc = 1.870 g/cm^3,/1 = 3.421 mm^-1, F（000） = 512, R = 0.0363 and wR = 0.0971; and those for 2： C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P21n, a = 7.739（5）, b = 10.668（7）, c = 11.008（7） A,β = 96.943（3）°, V = 902.1（11） A^3, Z = 2, Dc = 1.981 g/cm^3,/1 = 4.499 mm^-1, F（000） = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe（Ⅲ） ion is in a nearly regular octahedral environment. The title complexes can be described as two- dimensional （2-D） stair-like structures, which are further connected by hydrogen bonds to form three-dimensional （3-D） frameworks.

Synthesis and Crystal Structure of a Novel Heterometallic Complex with 1,2,4,5-Benzenetetracarboxylic Acid and 1,3,5-Tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene

A novel heterometallic complex,[Zn4Ni（OH）2（btec）2（titb）2（H2O）2]·2H2O（1）（H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris（imidazol-1-ylmethyl）-2,4,6-trime-thylbenzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817（10）,b=11.878（11）,c=14.569（14）,α=71.762（12）,β=76.122（13）,γ=71.493（13）°,V=1665（3）3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F（000）=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections（Ⅰ 2σ（Ⅰ））.In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.

A Copper(Ⅱ)-cadmium(Ⅱ) Heterometallic Hexanuclear Complex:[Cd_4Cu_2(pdc)_4(H_2O)_(14)](H_3pdc=3,5-Pyrazoledicarboxylic Acid)

The title complex 1,[Cd 4 Cu 2 （pdc） 4 （H 2 O） 14 ] （H 3 pdc=3,5-pyrazoledicarboxylic acid）,has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235（10）,b=1.27935（18）,c=1.28569（17） nm,α=112.633（2）,β=102.971（3）,γ=97.089（2）o,V=0.9673（2） nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ（MoKα）=3.356 mm 1,F（000）=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I 2σ（Ⅰ）.In 1,two deprotonated 3,5-pyrazoledicarboxylic acids （pdc 3）,one copper（Ⅱ） ion and one cadmium（Ⅱ） ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium（Ⅱ） ions through chelating carboxylate groups to construct the copper（Ⅱ）-cadmium（Ⅱ） heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional （3D） supramolecular framework.

Synthesis and Structural Characterization of a Cyano-bridged Dinuclear Neodymium(III)-iron(III) Complex [Nd(DMSO)_5(H_2O)_2](μ-CN)[Fe(CN)_5]

A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

ABSTRACT A new lanthanumm-ironm complex [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4]·H2O 1 （DMSO = dimethylsulfoxide） has been prepared by a facile approach, ball-milling method, and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 9.7125（3）, b = 21.5336（7）, c = 14.3804（5）A, β = 93.242（3）°, C16H34FeLaN60O7S5, Mr= 777.55, V = 3002.8（2）A^3, Z = 4, Dc = 1.720 g/cm^3, S = 1.053, μ（MoKα） = 2.278 mm^-1, F（000） = 1564, R = 0.0490 and ωR = 0.1270. The crystal structure analysis of 1 reveals a slightly distorted squareantiprism eighffold-coordinated La（Ⅲ） ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4] species are held together via hydrogen bonds to form a three-dimensional framework.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex[La(betaine)_2(H_2O)_6Fe(CN)_6]·2H_2O

The title complex [La(betaine)2(H2O)6Fe(CN)6]?2H2O (betaine = (CH3)3NCH2CO2) has been synthesized and characterized by X-ray single-crystal structure analysis. The crystal crystallizes in monoclinic, space group P21/n with a = 15.793(5), b = 8.927(3), c = 22.257(7) ?, β = 110.147(5)o, C16H38FeLaN8O12, Mr = 729.31, Z = 4, V = 2946.0(15) ?3, Dc = 1.640 g/m3, μ(MoKα) = 1.988 mm-1, F(000) =1476, R = 0.0388 and wR = 0.0827 for 4237 observed reflections (I > 2σ(I)). The La3+ ion is nine-coordinated by one cyano nitrogen atom and eight oxygen atoms of two betaine and six water molecules. Each complex molecule is connected to form a 3D network structure by some O–H…O and O–H…N hydrogen bonds.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.

Synthesis,Structure and Magnetic Properties of Novel Carboxylato-bridged Pentanuclear Copper(Ⅱ)-Lanthanoid(Ⅲ)Complexes

Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.

Synthesis of Heterometallic Rare Earth(Ⅲ)-Cobalt(Ⅱ)Complexes and Their Application in Alternating Copolymerization of Cyclohexene Oxide and Carbon Dioxide

Comprehensive Summary Four heterometallic rare earth(Ⅲ)-cobalt(Ⅱ)complexes(rare earth=Y(1),Sm(2),Nd(3),La(4))stabilized by an o-phenylenediamine-bridged tris(phenolato)ligand(L)have been synthesized and characterized.In these tetranuclear complexes,one polydentate L coordinates to one rare earth(Ⅲ)ion,and one cobalt(Ⅱ)ion,respectively,while two rare earth ions are bridged by four acetate groups.These complexes were applied in the copolymerization of cyclohexene oxide and CO_(2),which showed good activity(TON up to 440)and high poly(cyclohexene carbonate)selectivity(>99%).Kinetic studies determined the equation as rate=k[CHO]1[CO_(2)]0[initiator]1,which proves a first-order dependence on initiator concentrations and implies a synergistic mechanism with rare earth and cobalt ions cooperating in epoxide ring-opening and chain propagation.

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {(NH_4)_2[Cd(H_2O)Fe(CN)_6]}_n:Synthesis and Crystal Structure

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.

Syntheses,Structures,and Luminescent Properties of New Zn~Ⅱ-Y~Ⅲ and Zn~Ⅱ-Ln~Ⅲ Schiff Base Complexes

Eight new ZnⅡ-yⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes： MZnL2（NO3）3 （M = Y （1）, La （2）, Pr （3）, Nd （4）, Eu （5）, Gd （6）, Dy （7）, Er （8）; L = 2-（（（2- （imidazo[1,5-a]pyridin-3-yl）phenyl）imino）methyl）-6-methoxyphenol）, have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses （EA）, single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1-8 suggested zine/ligand-centered emission at room temperature.

Sm（Ⅲ）-Bi（Ⅲ） Heterometallic Complexes with Aminopolycarboxylate Ligand： Structure, Thermal Stability and Spectral Property

Samnium（Ⅲ）-bismuth（Ⅲ） heterobimetallic complexes, SmBi（edta）（NO3）2·7H2O （1） and SmBi（dtpa）（NO3）·3.5H2O（2） （edta=ethylenediaminetetraacetate, dtpa=diethylenetriaminepentaacetate）, were synthesized and characterized by means of X-ray single crystal diffraction, X-ray powder diffraction, elemental analysis, ICP, FT-IR spectra and thermal analysis. The structure analysis revealed that 1 is in crystalline and 2 is in non-crystal state. Complex 1 crystallizes in monoclinic, space group P2（1）/n with a= 1.2622（2） nm, b=0.81157（15） nm, c=2.3634（5） nm, β= 105.340（2）°, V=2.3347（8） nm3, Z=4, Dc=2.563 gocm^-3,μ=10.125 mm-1. Bridging edta4 anions between Bi（Ⅲ） atoms and Sm（Ⅲ） atoms result into infinite 3D network structure. Thermal decomposition of the two complexes proceeds in similar stages, i.e., dehydration, pyrolysis of ligand, and decomposition of salt, and the final residue is oxide. In addition, the spectral properties have been studied through FL spectra and UV-Vis DRS. The two complexes exhibit one broad band Bi 6s6p-6s2 emission under UV excitation and the characteristic Sm3＋ ion 4G5/2→6Hj/2 （J= 5, 7, 9, 11） transitions under visible light excitation, respectively.

Di- and tetranuclear heterometallic CuⅡ-LnⅢ complexes (Ln = Gd and Dy): Synthesis, structure and magnetic properties

Four 3d-4f heterometallic complexes, [CuⅡ-LnⅢ(bpt)2(NO3)3(MeOH)] (Ln = Gd, 1; Dy, 2; bptH = 3,5-bis(pyrid-2-yl)-l,2,4- triazole), [CuⅡ-LnⅢ(μ-OH)2(bpt)4C14 (H2O)2]·6H2O (Ln = Gd, 3; Dy, 4), have been synthesized under solvothermal condi- tions. X-ray structural analyses reveal that 1 and 2 are isostructural while 3 and 4 are isostructural. In each complex, the copper and gadolinium or dysprosium ions are linked by two triazolate bridges and form a CuⅡ-LnⅢ dinuclear unit. The intramolecu- lar Cu-Ln distances are 4.542, 4.525, 4.545 and 4.538 ] for 1, 2, 3 and 4, respectively. Two dinuclear CuLn units are bridged by two OH- groups into the zig-zag tetranuclear {cunzLnm2} structures with the Ln(Ⅲ)...Ln(Ⅲ) distances of 3.742 and 3.684 for 3 and 4, respectively. Magnetic studies show that the antiferromagnetic CulI-Lnm interactions occur in 1 (Jcu = -0,21 cm-1) and 2. The antiferromagnetic interaction occurs in complex 3 with JcuGa = -0.82 cm-1 and JcdGd = --0.065 cm-1, while domi- nant ferromagnetic interaction occurs in complex 4.

Synthesis and Crystal Structure of a Cyano- bridged Bimetallic Complex[La(DMSO)_3(H_2O)_3- Cr(CN)_6]·H_2O (DMSO = Dimethylsulfoxide) with One-dimensional Chain Molecular Structure

The title complex [La(DMSO)3(H2O)3Cr(CN)6]H2O was obtained by the reaction of LaCl37H2O, DMSO and K3[Cr(CN)6] in aqueous solution on a hot water bath. The crystal crystallizes in orthorhombic, space group P212121 with a = 9.827(3), b = 15.037(4), c = 17.633(5) ? C12H26CrLaN6O7S3, Mr = 653.48, Z = 4, V = 2605.7(13) ?, Dc = 1.666 g/m3, (MoKa) = 2.314 mm-1, F(000) = 1300, R = 0.0205 and wR = 0.0481 for 5038 observed reflec- tions (I > 2s(I)). La3+ ion is eight-coordinated by three DMSO molecules, three H2O molecules and two [Cr(CN)6]3- units. The structure of the title complex possesses a cyano-bridged one- dimensional zigzag chain structure with alternating La(DMSO)3(H2O)3 and Cr(CN)6 moieties, which are linked by some hydrogen bonds to form a 3D network structure.

Synthesis and Structural Determination of a Novel Heterometallic Complex [Sb2（edta）2-μ4- Co（H2O）2]·5.15H2O

The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.

Design and Synthesis of Al_(7)Ni_(2) Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies

The synthesis of heterometallic aluminum-based materials is challenging yet attractive,due to their potential applications in optics,catalysis,magnetism and semiconductor device.We have now successfully synthesized two Al,Niz heterometallic clusters bearing different peripheral alkoxide ligands through a heterometal substitution strategy.

Synthesis,Structures,and Fluorescence Property of a Novel Heterometallic Complex Constructed by Imidazole

A novel heterometallic complex constructed by imidazole ligand,CoZn(C3N2H3)4(1),has been synthesized under hydrothermal conditions.Compound 1 was characterized by IR spectra,thermal analysis,powder X-ray diffraction and single-crystal X-ray diffraction.Single-crystal X-ray diffraction studies reveals that compound 1 is in the tetragonal system,space group I41cd with a=23.4371(5),b=23.4371(5),c=12.4430(7)?,V=6834.9(4)?3,Z=16,C12H12CoN8Zn,Mr=392.60,Dc=1.526 g/cm^3,F(000)=3152,μ=2.381 mm–1,R=0.0323 and w R=0.0789.The CoZn(C3N2H3)4 is one-dimensional heterometallic molecular chains,which are further extended into a 3D open framework.Moreover,the solid-state fluorescence property of the complex has also been investigated at room temperature.

Ag(Ⅰ)、Pd(Ⅱ)异核金属簇合物的制备和晶体结构研究

The complexes of [Ag2Pd2(μ-dppm)2(μ-S2CNC4H8)2(μ3-S2CNC4H8)2](SbF6)2·Et 2O (1) and [AgPd(S2CN C4H8)(μ-dppm)2](SbF6)·H2O (2)were synthesized and their single crystal structures were determined by X-ray diffraction. The complex 1 is monoclinic system, space group P21/c with a=1.14370(3)nm, b=1.39025(4)nm, c=2 .93579(8)nm, β=95.173(1)°, V=4.6490(2)nm3, Z=4, Dc=1.716g·cm-3, μ(MoKα)=16 82cm-1, F(000)=2384, Mr=2401.98, R=0.0662, wR=0.1302. The complex 2 is monoclin ic system, space group Cc with a=2.74136(6)nm, b=1.04317(2)nm, c=2.523990(10)nm, β=95.173(1)°, V=4.6490(2)nm3, Z=4, Dc=1.716g·cm-3, μ(MoKα)=1682cm-1, F(0 00)=2384, Mr=2401.98, R=0.0662, wR=0.1302. CCDC: 1, 213613; 2, 213612.