Hydrothermal Synthesis,Crystal Structure and Thermal Analysis of a Dinuclear Complex Cd_2(3,5-Dinitrobenzoate)_4(pyridine)_4

A dinuclear complex Cd2（dnba）4（pyridine）4 （dnba = 3,5-dinitrobenzoate） has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 （Mr = 692.83） crystallizes in monoclinic, space group P21/n with a - 12.0344（14）, b = 10.5752（13）, c = 21.578（3） A, β = 104.150（2）°, V = 2662.8（6） A^3, Z = 2, D, = 1.728 g/cm^3,μ（MoKa） = 0.897 mm^-1, F（000） = 1384, S = 1.016 and （△/σ）max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd（Ⅱ） centers to give the dinuclear structure. The other coordination positions of Cd（Ⅱ） are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.

Synthesis and Characterization of Two Novel High Valent Dinuclear Complexes with a Triphenolate Ligand Bearing Functional Groups

Two novel high valent complexes [M2(III, III)L(μ-OAc)2]·PF6 (M=Mn, Fe; 9) were prepared, where L was the tri-anion of 2,6-bis{[(2-hydroxy-3-(morpholin-4-yl methyl)-5-tert- butyl benzyl)(pyridyl-2-methyl)amino]methyl}-4-methyl phenol which contained additional phenolic, tert-butyl and morpholin-4-yl methyl groups compared to its parent [Mn2(II, II)(bpmp) (μ-OAc)2]·ClO4 (10). These improvements decreased the difference between the new model and (Mn)4 cluster (OEC in nature).

A Novel Mixed Ligand Dinuclear Complex of Cobalt (II): Synthesis, Characterization and Magnetic Studies

A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.

Hydrothermal Synthesis and Crystal Structure of a Novel Dinuclear Co(Ⅱ) Complex:[Co2(2,2'-bpy)_2(μ-L)_2(L)_2(μ-H_2O)](HL=4-Chlorobenzoic Acid)

A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537（5）, b = 16.212（3）, c = 15.306（3） A, β= 124.37（3）°, V= 4616.1（16）A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F（000） = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2（2,2＇-bpy）2（μ-L）2（L）2（μ-HaO）] molecules. Each Co（Ⅱ ） atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co（Ⅱ） atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.

Synthesis and Characterization of a New Ligand 2-(4, 5-Dihydro-2-thiazolyl)-6-methoxylbenzothiazole and Its Dinuclear Co(II) Complex

A new ligand 2-（4,5-dihydro-2-thiazolyl）-6-methoxyl benzothiazole and its new dinuclear Co（II） coordination complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 （1） have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co（II） salt with 2-（4,5-dihydro- 2-thiazolyl）-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C-H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288（12）, b = 10.5273（15）, c = 10.822（2）, α = 93.416（3）, β = 90.864（3）, γ = 94.890（3）o, V = 943.60（2）3, Z = 2, Dc = 1.758 g/cm3, F（000） = 498 and μ = 1.840 mm-1. The final complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co（II） ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.

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.

Template Synthesis and Structure of Dinuclear Zinc Complex with Three Kinds of Pyrazole Ligands

The title complex[Zn_2L(C_5H_7N_2)_2(C_5H_7N_2·HClO_4)_2](L=1,2-di(3', 5'-dimethylpyrazolyl) formylhydrazine and C_5H_7N_2= 3 , 5 dimethylpyrazole anion) has been synthesized by template reaction, in which carbonhydrazine, 2, 4-pentanedione and zinc perchlorate hexahydrate were used as the original materials. The crystals of complex with formula C_(32)H_(46)N_(14)O_(10)Cl_2Zn_2 (Mr=988.46) are triclinic,space group P1,a= 8.275 (2),b=11.523 (3),c= 12.872(5), a=69. 90(3),β= 69.79 (2), γ=83. 52 (2)°,V=1081.6(6),Z=1,Dc=1.524g/cm￣3,μ=13.265cm￣(-1),F (000)=510. The final refinement is converged with R= 0.057. The results indicate that in one complex molecule there are three kinds of pyrazole rings all directly coordinated to the central Zn atom; and each zinc atom possesses a five-coordinated polyhedron.

Synthesis, Crystal Structure, Fluorescence, Thermal Stability and Magnetic Properties of the Dinuclear Manganese(Ⅱ) Complex [Mn_2(L)_2(2,2'-bipy)_2(H_2O)_5]_2·3H_2O

A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944（10）, b = 21.939（2）, c = 25.628（3） A, a = 108.429（3）, β = 100.613（4）, 7 = 102.821（3）°, V = 4997.9（9） A3, Dc= 1.355 g/cm^3, Z = 2, F（000） = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2（L）2（2,2＇-bipy）2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.

Solid-state Synthesis at Low-heating Temperature and Crystal Structure of a Dinuclear Molybdenum Complex with Oxalate Ligand[Bu_4N]_2[Mo_2O_2(OH)_2Cl_4(C_2O_4)]

The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.

Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.

Crystal Structure,Fluorescence and Thermal Stability Properties of a Dinuclear Copper(Ⅱ) Complex[Cu_2(L)_2(phen)_2]-5H_2O(H_2L = Bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid)

A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.

Synthesis and Structure of a New Dinuclear Uranyl Complex

With a heptadentate compartmental Schiff-base ligand H3L (1, 3-di[o-(salicylimino) ph- enoxyl]-2-propanol), a new binuclear diuranyl complex [(UO2)2L(OH)]?DMF, C38H45N5O13U2, was synthesized and the crystal structure was determined by X-ray diffraction techniques. The coordination geometry are two pentagonal bipyramids. In each pentagon four kinds of U-O (phenoxido, hydroxo, alkoxo and ether oxo) bonds are discussed.

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

Four dinuclear amino acid cadmium（II） complexes [Cd2（tren）2（dl-alaninato）]（ClO4）3·H2O（I）, [Cd2（tren）2· （l-alaninato）]（ClO4）3·H2O（II）, [Cd2（tren）2（dl-phenylalaninato）]（ClO4）3（III） and [Cd2（tren）2（l-phenylalaninato）]· （ClO4）3（IV）, constructed from mixed ligands of tris（2-aminoethyl）amine（tren） and racemic or natural amino ac ids（amino acids=dl or l-alanine, and dl or l-phenylalanine）, have been synthesized and characterized by X-ray crys tallography. The structural analysis of complexes I and III reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual （N,O,O′）-bridged mode, resulting in asymmetric chromo phores of CdN4O and CdN5O in complex I, CdN4O2 and CdN5O in complex III, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the dias tereoselectivity of the reaction favors the formation of the syn-isomers.

A New Dinuclear Cu(Ⅱ) Complex of a Ligand with Benzimidazole Group─Synthesis and Crystal Structure

A new dinuclear copper complex, [Cu（C9H11N3）Cl2]2（C18H22Cl4Cu2N6）, has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic P1^- space group with a = 7.526（3）, b = 9.473（4）, c = 9.535（3）A, α = 117.214（10）, β = 108.251（9）, γ = 91.560（6）°, V = 562.3（4）A^3, Z = 1, Mr = 591.30, F（000） = 298, Dc = 1.746 g/cm^3, μ（MoKα） = 2.385 mm^-1, the final R = 0.0577 and wR = 0.1248 for 2188 unique reflections with 1629 observed ones （Ⅰ〉 2σ（Ⅰ））. In the title complex, each copper（Ⅱ） atom is located at the center of a distorted trigonal bipyramid of five coordination atoms （two nitrogen and three chlorine atoms）. Two copper（Ⅱ） atoms were bridged by two chlorine anions （Cl（2） and Cl（2a）） to form a Cu（Ⅱ）-Cu（Ⅱ） binuclear entity with the distance between two copper（Ⅱ） atoms of 3.398 （A）.

Synthesis and Crystal Structure of a Novel Dinuclear Copper(Ⅱ) Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper（Ⅱ） complex [CuL（NO3）]2·2MeOH was obtained by the coordination reaction of Cu（NO3）2·3H2O with ligand HL （HL=N-（methyl-2-benzimidazol- methylidene）-2-hydroxyaniline）. The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535（3）, b=10.009（3）, c=10.666（4） , α=104.303（4）, β=100.105（4）, γ=115.917（4）o, V=839.0（5） 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F（000）=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper（Ⅱ） complex units [CuL（NO3）]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper（Ⅱ） units.

Crystal Structures of Dinuclear Copper(Ⅱ) Complexesof bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.

Hydrothermal Synthesis,Crystal structure,DFT and Application of a Dinuclear Cadmium(Ⅱ) Complex Based on NPHSNPAB

A new dinuclear cadmium（Ⅱ） complex,[Cd（NPHSNPAB）（H_2O）_2（CH_3CH_2OH）]_2（1）,was synthesized by the hydrothermal reaction of N-phenyl-2-[2-hydroxyl-3-sulfo-5-nitrophenylazo]butadiene-1,3（NPHSNPAB） and Cd（NO_3）_2·4H_2O,and characterized by elemental analysis,infrared,UV-visible,fluorescence,thermal behavior and single-crystal X-ray diffraction. For this complex： C_（36）H_（42）Cd_2N_8O_（22）S_2,Mr = 1227.74,triclinic system,space group P1,a = 7.555（9）,b = 12.006（14）,c = 13.943（16） ？,α = 67.955（2）,β = 88.573（2）,γ = 77.550（2）o,V = 1142.5（2） ？~3,Z = 2,Dc = 1.784 g/cm^3,λ = 0.71073 ？,F（000） = 620,S = 1.125,R = 0.0460 and w R = 0.1159 for 3949 observed reflections with I 〉 2（I）. X-ray diffraction analysis reveals that the central Cd（Ⅱ） ion is bound by six oxygen atoms,forming a slightly distorted octahedral geometry. Density functional theory of complex 1 was studied. Noticeably,the application of 1 on metallic yarn got good effect.

A Novel Sandwich-type Dinuclear Complex for High-capacity Hydrogen Storage

From density functional theory （DFT） calculations, we predicted that the sandwich-type dinuclear organometallic compounds Cpffi2 and Cp2Sc2 can adsorb up to eight hydrogen molecules respectively, corresponding to a high gravimetric storage capacity of 6.7% and 6.8% （w）, respectively. These sandwich-type organometallocenes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions.

基于共轭驱动的Cu(Ⅱ)氧化仲胺合成氯桥联双核Cu(Ⅰ)配合物

现行的实验教材中缺乏双核桥联配合物合成的实验,关于仲胺合成和Cu(Ⅱ)氧化性的知识也较少。本实验从有机化学理论知识中的基本反应出发,设计了两条路线合成目标仲胺配体,即基于亲核取代反应的路线一和亲核加成缩合-还原的路线二。运用配位化学原理及有机化学中的共轭驱动效应,使弱氧化性的Cu(Ⅱ)将仲胺氧化成共轭的芳香亚胺(希夫碱)结构,同时利用希夫碱的配位作用和氯离子的桥联配位作用形成稳定的氯桥联双核Cu(Ⅰ)配合物。为适应普通高校的实验教学条件,本实验还设计了一套操作简单、现象直观的Cu(Ⅰ)配合物中铜离子价态的鉴定实验。本实验所涉实验原理既包含基础化学反应知识,又体现最新的科学研究成果,反应条件温和、实验现象直观、重现性好、收率高,能有效提高学生的综合实验操作技能,锻炼学生的有机合成、配位合成能力。

Syntheses, characterization, and luminescence of two lanthanide complexes [Ln_2(acetate)_6(H_2O)_4]·4H_2O (Ln=Tb(1), Sm(2))

Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.