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.

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.

一例U-Ag杂金属半刚性羧酸配体配合物的制备及性质研究

为了深入研究锕系元素的配位行为,基于半刚性羧酸配体3-(羧基甲氧基)苯甲酸(H_(2)L),合成了一个三维结构的U-Ag杂金属配合物[(L)(HL)Ag(UO_(2))](简称UAgL)。通过X-射线单晶衍射、红外光谱、紫外光谱及X-射线粉末衍射对其晶体结构进行了表征,结果显示,配合物UAgL中铀原子处于稍变形的五角双锥配位环境中,银原子则处于五配位的四方锥配位环境中。铀酰离子中的氧原子参与配位且处于轴向位置,完全脱质子的配体L和部分脱质子的配体HL则采取两种配位模式将铀中心与银中心连接成二维层状结构,层状结构之间又通过铀酰氧原子连接成三维的网络结构。进一步探讨了配合物UAgL的热稳定性和在室温下的固态荧光性质,认为其可作为潜在的光致发光材料。

Heterometallic Mg-Ni-Mg Complex Promoted Hydrosilylation of Alkenes: Catalytic Performance and Intermediates Characterization

Background and Originality Content The catalytic hydrosilylation of unsaturated hydrocarbons,facilitated by transition metal(TM),is widely recognized as a proficient technique for the synthesis of high-value organosilicon compounds'ti-4l over the past few decades,the most dominant cata.lysts in hydrosilylation processes have been constituted by pre-Ccious metar complexesroceinerecent vears omore sustainabile earth-abundant metal catalysts have received increased attentionj2-14l The classcal mechanism of transition metal-catalyzed hydrosilylation is generally accomplished through a series of fundamental processes(Scheme 1a),including(i)coordination and oxidative addition of Si-H bond to a low-valent metal center to form e.g.,o-complex or silyl metal hydride;(ii)insertion of.C-C multipe bonds intometal-hdridelsior metal-silicon bond;jiol and(ii)reductive elimination that forwards the hydrosilylated product with Markovnikov or anti-Markovnikov selectivity.

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.

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.

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.

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 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.

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.

[Mn(H_2O)_6][Bi(edta)]_2·2H_2O的合成与晶体结构

以MnCO3与多胺羧酸铋反应,合成了含铋多金属配合物[Mn(H2O)6][Bi(edta)]2.2H2O,通过元素分析和红外光谱对配合物的组成和结构进行了表征。用热重-差热手段研究了配合物的热分解过程,用X射线单晶衍射法测定了其晶体结构。[Mn(H2O)6][Bi(edta)]2.2H2O属单斜晶系,C2/c空间群,晶胞参数:a=2.37013(4)nm,b=0.87111(2)nm,c=1.61082(3)nm,β=97.273(1)°,Z=4,Mr=1193.46,V=3.299.01(11)nm3,Dc=2.403g.cm-3,μ=11.123mm-1,F(000)=2284,R1=0.0210,wR2=0.0567。大量分子间氢键将整个连接起来形成无限3-D结构。

基于配合物配体策略的Cu-Cd异核配位聚合物的合成与晶体结构

利用小分子配合物[Cu(2-mpac)2(H2O)]·3H2O(1)作为配合物配体,以其两侧未配位的羰基氧原子与金属配位合成了一个Cu-Cd异核配位聚合物[Cu(2-mpac)2(H2O)2Cd(H2O)4(NO3)2]n(2)(2-mpac=5-methyl-2-pyrazinecarboxylic acid),并利用元素分析、红外光谱以及X射线单晶衍射法对标题化合物进行了表征.晶体学数据:三斜晶系,P-1空间群,a=0.7654(7)nm,b=0.8903(8)nm,c=0.9745(9)nm,α=116.116(1)°,β=98.408(1)°,γ=90.335(1)°,V=0.5880(9)nm3,Z=1,S=1.053,最终残差因子[I>2σ(I)]R1=0.0280,wR2=0.0718,对于全部数据R1=0.0305,wR2=0.0741.

配合物LaBi(edta)(NO_3)_2·7H_2O的水热合成、表征及热分解研究

用NH4Bi(edta).2H2O配合物和硝酸镧按1∶1的物质的量比在150℃条件下,通过水热方法合成了含铋(Ⅲ)和镧(Ⅲ)双金属配合物LaBi(edta)(NO3)2.7H2O。用元素分析仪和滴定分析法确定了产物的组成,用FT-IR、XRD和TG-DSC对产物进行了表征。该配合物为单斜晶系,晶胞参数:a=1.0399nm,b=1.2199nm,c=2.3617nm,β=93.999°。热稳定性研究发现该配合物分解时经过脱水、配体热分解、硝酸盐分解,最后在621℃稳定,残余物为La/Bi氧化物LaBiO3.68。

三核杂金属配合物[Sb_2(edta)_2Gd(H_2O)_4]NO_3·3H_2O的合成与表征

以乙二胺四乙酸(H4edta)、三氧化二锑、氧化钆为主要原料,在水溶液中反应合成了锑(III)和钆(III)的三核杂金属配合物[Sb2(edta)2Gd(H2O)4]NO3·3H2O,用元素分析、红外光谱、X射线粉末衍射和热分析等方法对配合物的组成和结构进行了表征。X射线粉末衍射数据指标化计算结果证实该配合物晶体结构属于单斜晶系,晶胞参数为:a=11.259,b=9.689,c=20.489,β=94.099°。其热分解过程包括失水、配体及NO-3的氧化分解过程,最后完全形成金属氧化物。

两个3d-4f杂核配合物[Fe(phen)_3]_2[FeLn(H_2O)(tiron)_3]·6H_2O的合成、晶体结构和磁性(Ln=Ho~Ⅲ,Yb~Ⅲ)

Ln2O3、硝酸铁、邻菲罗啉和钛铁试剂(tiron)通过水热法自组装合成了2个异质同晶的3d-4f杂核配合物[Fe(phen)3]2[FeLn(H2O)(tiron)3]·6H2O,其中,Ln=HoⅢ(1)和YbⅢ(2)。X-射线单晶衍射分析表明,晶体属立方晶系,P213空间群。3个tiron4-配体利用酚氧桥联Ln3+和Fe3+形成具有C3对称性的[FeLn(H2O)(tiron)3]6-异双核配位单元,其中七配位的Ln3+呈现一种畸变的单帽反三棱柱配位构型。配阳离子[Fe(phen)3]3+通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成三维的超分子。在2～300 K温度范围内测试了配合物的变温磁化率,结果表明,Ln(Ⅲ)-Fe(Ⅲ)之间存在反铁磁性相互作用。

功能三联吡啶异金属六核配合物的合成与表征

目的研究新型多核异金属配合物的一步合成方法及配合物的结构特征。方法将FeCl_3,CdCl_2·2.5H_2O与4′-(3-吡啶基)-2,2′:6′,2″-三联吡啶在甲醇溶剂中自组装反应,并利用元素分析、红外光谱、X-射线单晶衍射结构分析等方法对所得化合物进行了表征。结果包含Fe~Ⅱ,Cd~Ⅱ双金属的六核配合物[Fe(3-pytpy)_2Cd_2Cl_6]_2·2CH_3OH(1)单晶被合成。结论 Fe~Ⅲ在反应过程中被还原为Fe~Ⅱ,每个Fe~Ⅱ与两个3-pytpy形成[Fe(3-pytpy)_2]^(2+)构建单元,该单元中的两个未配位的氮原子桥联五、六配位的Cd~Ⅱ形成Cd…Fe…Cd三核单元,三核单元再通过双氯桥联成二聚体。配合物通过弱氢键形成二维超分子结构。