Synthesis of a Novel Aromatic Diamino-bridged Bis(β-cyclodextrin) and its Inclusion Complexation with Dyes Molecules

A novel brideed bis（β-cvclodextrin）, 4, 4＇-diaminodiphenyl ether-bfiged-bis （6-aimino-6-deoxv-β-cyclodextrin） 3, has been synthesized and its inclusion complexation behavior with three linear＇guest dyes （AR, NR and MB ） has been investigated by. means of fluorescence spectrometry. The-result obtained demonstrated that the novel bridged bis（β-cyclodextnn） showed much higher affinities towards guest dyes than native β-cyclodextrin.

Electrocatalytic oxidation of methanol at platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes

The electrocatalytic oxidation of methanol at the platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes (Eu-Fe film) was investigated for the first time by cyclic voltammetry.Compared with the bare platinum electrode,the results showed that the modified electrode had excellent electrocatalytic activity for the oxidation of methanol;the oxidation peak potential shifted more negatively and the peak current increased about twenty times.The electrooxidation of methanol at the modified elect...

Synthesis and Characterization of the First Dinuclear Europium(Ⅱ) Complex Supported by Carbon-Bridged Biphenolate Ligand

Anhydrous EuCl3 reacted with sodium carbon-bridged biphenolate LNa2[ L = 2,2＇-methylene bis（6-tert-butyl-4- methyl-phenoxo ] in a 1 ： 1 molar ratio in THF in the presence of HMPA （HMPA = hexamethylphosphoric triamide）, then the product formed in situ was reduced by Na-K alloy to generate the divalent carbon-bridged biphenolate europium complex [ LEu （HMPA） 2 ] 2 （THF） 4 （ 1 ） in a good isolated yield. Complex 1 was fully characterized by elemental analysis, NMR and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P2 1/c space group, a=1.6521（3） nm, b=2.8274（3） nm, c=1.2074（2） nm, β=111.723（6）°, V=5.2393（14） nm^3, Z=2, Dc= 1.259 mg·m^-3, μ = 1.304 mm^-1, F（000） = 2092, R = 0.0815, wR = 0. 1723. Complex 1 is a dimer with two Eu - O bridges. The coordination geometry of each europium atom can be best described as a distorted trigonal bipyramid.

Preparation and Characterisation of Cyclopentadienyl Tetramethylethene－bridged Dicyclopentadienylsamarium（Ⅲ）Tetrahydrofuranate Complexes

The complexes of cyclopentadienyl tetramethylethenebridsied dicyclopentadienylsamarium (Ⅲ) tetrahydrofuranates, Me4C2(C5H4)2LnC5H5 (THF) (Ln = Nd, Sm, Gd, Yb) were synthesized and characterized by elemental analysis, IR, 1HNMR, thermogravimetry and MS. The crystal structure of Me4C2(C5H4)2SmC5H5 was determined by X-ray diffraction method. The crystal belongs orthorhombic space group Cc2a. with a =1 . 1696(6) nm, b =1 .2539(5) nm, c = 2.9432(15) nm, V= 4.316 (4) nm3, Z= 8 and Dc = 1 . 54 g . cm-3.

The Assembly and Molecular Structure of a Novel One-dimensionalCyanide-bridged [Ni(pn)_2Ni(CN)_4]_n·nH_2 O Complex

The synthesis, structure and characterization of a new one-dimensional cyanide-bridgedcomplex [Ni(pn)_2Ni(CN)4]n'nH2O (where pn = 1,2-diaminopropane) are described. The structure ofthis complex consists of a one-dimensional polymeric chain-Ni(pn)2-NC-Ni(CN)2-CN-Ni(pn)2- inwhich the Ni(II) centers are linked by two CN groups.

One and Two-dimensional Structures of a New Oxamido Copper(II) Complex with Phthalato Bridged

A new o-phthalato-bridged oxamide copper（Ⅱ） complex 1, {[Cu2（oxap）]（pht）. 4H2O}n （oxap=N, N＇-bis（2-aminopropyl）oxamide, pht= phthalate dianion）, has been prepared and structurally characterized. It crystallizes in monoclinic, space group C2/c with a=23.424（4）, h=7.9696（14）, c=15.727（3）A°,β=129.617（2）°, C16H28Cu2N4O10, Mr=563.50, V=2261.6（7） A°, Z=4, Dc=1.655 g/cm^3, μ（MoKα）=1.939 mm^-1, F（000） = 1160, the final R=0.0393 and wR=0.0928 for 1707 observed reflections with I〉2σ（1）. Single-crystal X-ray analysis reveals that 1 displays a one-dimensional zigzag chain structure, in which each Cu（oxap） moiety adopting trans-conformation is connected by ,μ1,6-phthalate anion bridges, and these zigzag chains are further linked by another ,μ1,6-phthalate anion bridge to form a 2D sheet structure. The polar guest water molecules reside in the inter-and intrasheets to stabilize the whole crystal structure.

Designed Syntheses and Crystal Structures of Two Cis-cyanide Bridged Trinuclear Complexes

Two cyanide bridged trinuclear compounds [Fe（bpy）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·DMF 1 and [Fe（Phen）2（CN）2]·[Cu（Cyclam）]2（ClO4）4·2CH3CN·4H2O 2 （Bpy = 2,2＇- bipyridine, Phen = 1,10-phenanthroline, Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, and DMF = N,N-dimethylformamide） have been synthesized by using mononuclear [Fe（Phen）2（CN）2]·2H2O and [Fe（bpy）2（CN）2]·3H2O as precursors. These two complexes crystallize in monoclinic space groups P21/c and C2/c, respectively. For 1, a = 25.164（2）, b = 12.0405（11）, c = 20.4433（15） A, β = 91.948（3）°, V = 6190.5（9） A^3, Z = 4, Mr = 1418.90, Dc = 1.522 g/cm^3, F（000） = 2936, μ = 1.161 mm^-1, the final R = 0.0722 and wR = 0.2011 for 10779 observed reflections （I 〉 2σ（I））. For 2, a = 43.5945（0）, b = 11.8447（0）, c = 29.5637（2）A, β = 120.430（11）o, V = 13162.76（9） A^3, Z = 8, Mr = 1518.48, Dc = 1.533 g/cm^3, F（000） = 6288, μ = 1.101 mm^-1, the final R = 0.0711 and wR = 0.1783 for 11262 observed reflections （I 〉 2σ（I））.

Hydrothermal Synthesis, Crystal Structure and Fluorescence Properties of a Three-dimensional Triply-bridged Binuclear Zinc(Ⅱ) Complex [Zn_2(Mba)_3(Phen)_2EtOH)]·ClO_4

The novel complex [Zn2（Mba）3（Phen）2EtOH）]·ClO4 （Hrnba = methoxybenzoic acid, Phen = 1,10-phenanthroline, EtOH = ethanol） was synthesized by hydrothermal reactions, and its structure was determined by X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 1.15362（1）, b = 1.3655（3）, c = 1.61451（1） nm, α= 72.842（2）, β = 83.259（3）, y = 72.083（2）°, V = 2.3112（6） nm3, Z = 2,μ（MoKa） = 11.71 cm-1, F（000） = 1120, R = 0.0552 and wR = 0.1157 （I 〉 2σ（I））. The two centric zinc（H） ions in the complex locate in a distorted octahedral coordination geometry and a distorted trigonal bipyramid coordination geometry, respectively. Two bridging bidentate carboxyl groups and a μ2-O carboxyl group from three methoxybenzoic acids act as the bridge to link two Zn（Ⅱ） ions. The asymmetric units are connected by π-π packing interactions between aromatic rings to form a three-dimensional supramolecular network. The experimental results show a good fluorescence property for the complex.

Crystal Structure of Bridged Dimer Complex of [Yb (H_2O)) (acac)_2 (Ac)]_2

The title complex C24H38O14Yb2(Mr=896. 62 ) crystallized in orthorhombic system, space group Pbcn with unit cell dimensions a=13. 478 (4), b=16. 161(7), c=15. 110(5); V=3291. 2(2); Z=4; F(000) = 1736; Dc=1. 810g. cm-3;μ= 17. 5 cm-1 (MoKa). The final R and Rw are 0.061 and 0.058 respectively. The title complex is a bridged dimer. The ligands that bridge two Yb(Ⅲ) centerions are the two acetatos in the complex and every Yb(Ⅲ) ion is eight-coordinated, being bonded to one O atom of one H,O molecule, four O atoms of two acetylacetonatos,two O atoms of an acetato and one O atom of another acetato. The coordination polyhedron of the Yb(Ⅲ) ion in the title complex is a dodecahedron.

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5- Benzenetetracarboxylato Trivalent Anion

The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

TRIPLY BRIDGED BINUCLEAR COMPLEX OF OXOMOLYBDENUM(Ⅴ)WITH MERCAPTOPHENOLATE LIGANDS

Reaction of(n-Bu_4N)_xNa_(4-x)[a-Mo_8O_(26)](x=1-4)and mpH_2(mpH_2=o-mercaptophenol) leads to the formation of compound(n-Bu_4N)[Mo_2O_3(mp)_3Na(EtOH)_2(MeOH)],It crystallizes in the space group P2_1/n with four molecules per unit cell.The cell dimension is a=12.776(3),b=14.154(5),c=26.281(7)(?)=95.50(2)°,V=4730.5 (?),d_c=1.407 g/cm^3.Full-matrix refinement of 496 parameters on 3348 reflection data gave final R(R_w) value of 0.072(0.072).The two oxomolybdenum-mercaptophenolate,units are triply bridged by an inorganic oxygen atom and a doubly bridging mp^(2-)ligand.

SYNTHESIS AND STRUCTURE OF A NOVEL INFINITE-LAYER COPPER(Ⅱ)COMPLEX BRIDGED BY OXAMIDE AND PYRIMIDINE

The complex polymer[Cu_2(oxap)(pyr)_2]_n(ClO_4)_(2n),where oxap^(2-)stands for N,N' -bis(2—aminopropyl)oxamide,have been synthesized.It crystallizes in monoclinic system, space group P2_1/C,with a=8.721(2),b=8.679(2),c=16.741(2),β=98.59(0),Z=4.The least-square refinement coverged at R=0.054,R_w=0.055 with 1869 unique reflections.The whole structure of the complcx consists of layers of two-dimensional network arraying along a-axis with perchlorate ions interspersed in the gap between layers.Inside the layer. trans-oxamide-bridged copper(Ⅱ)dimers connected by pyrimidine in an asymmetric fashion spread out along be plane to form an infinite two-dimensional network.

SYNTHESIS AND CRYSTAL STRUCTURE OF THE FIRST THREE DIMENSIONAL NETWORK CU(Ⅱ) COMPLEX BRIDGED BY BOTH OXAMIDE AND AZIDE

A novel three dimensional network complex polymer [Cu_4(oxen)_2(N_3)_3]_n(ClO_4)_n·2nH_2O, where oxen is N,N' -bis(2-aminoethyl)oxamide dianion, has been synthesized. It crystallizes in triclinic system, space group P, with a=11.486(2), b=11.706(3), c=12.291(3) , α=77.42(2), β=67.59(2), γ=77.96(2)°, and z=2. The least-square refinements converged at R=0.047, with 3416 observed unique reflections. The complex has a pronounced three-dimensional character and can be viewed as the tetranuclear asymmetric repeating units through inversion and translation operations to extend a three-dimensional network. The structure of Cu_4 asymmetric unit consists of two square planar and two square pyramidal Cu central atoms linked by both azide ligands in end-on and end-to-end bonding modes, and oxamidate bridge in trans conformation.

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 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.

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce（DMSO）4（H2O）3Fe（CN）6]·H2O 1 and [La（DMSO）4（H20）3Co（CN）6].H20 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1： C14H32CeFeN6O8S4, Mr= 736.67, monoclinic, space group P2 1/n, a = 14.952（1）, b = 13.7276（9）, c = 15.392（1） A, β= 108.288（1）°, V = 2999.6（4） A3, Z = 4, Dc= 1.631 g/cm^3, g = 2.304 mm^-1, F（000） = 1480, R = 0.0593 and wR = 0.1611; and those for 2： C14H32CoLaN6O8S4, Mr=738.54, monoclinic, space group P21/n, a = 14.945（3）, b = 13.731（3）, c = 15.300（3） A, β= 107.806（1）°, V= 2989.3（11） A^3, Z= 4, Dc = 1.641 g/cm^3, μ = 2.288 mm^-1, F（000） = 1480, R = 0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe（Ⅲ） or Co（Ⅲ） ion in a nearly regular octahedral environment The [LnM（CN）6（DMSO）4（H2O）3]·H2O （Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2） species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.

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 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.