Two New Cu(Ⅱ) Coordination Polymers Based on 2,5-Furandicarboxylic Acid and 2,2'-bipyridine:Synthesis and Crystal Structure

Two new Cu（II） coordination polymers, [Cu（FDA）（BPY）（H20）]n （1） and {[Cu（FDA）（BPY）（H2O）].2H2O}n （2） （H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2＇-bipyridine）, have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 7.5915（15）, b = 8.4050（17）, c = 24.204（6） A, β = 99.05（3）°, V= 1525.1（6） A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F（000） = 796, μ（MoKa） = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections （1 〉 2a（I））, R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660（18）, b = 8.9112（18）, c = 12.525（3） A, a = 88.41（3）, β = 69.38（3）, γ = 66.95（3）°, V = 845.2（3） A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, Mr. = 427.85, F（000） = 438, μ（MoKα） = 1.342 mm-1, Z = 2, R = 0.0290 and wR = 0.0690 for 2767 observed reflections （I 〉 2σ（I））, R = 0.0329 and wR = 0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.

Asymmetric Synthesis of Novel Axially Chiral 2,2＇-Bipyridine N,N＇-Dioxides Bearing α-Amino Acid Residues and Their Applications in Enantioselective Allylation of Aromatic Aldehydes with Allyltrichlorosilane

A series of novel axially chiral 2,2＇-bipyridine N,N＇-dioxides bearing C1 or C2-symmetry have been synthesized by the use of enantiopure a-amino acids as chiral sources. The absolute stereochemistry of the axial chirality of these organocatalysts has been clearly assigned by means of CD measurements together with literature protocols. The reactivities and enantioselectivities of these organocatalysts have been examined in the reactions of aromatic aldehydes with allyltrichlorosilane, thus providing the desired products with moderate yields and enantioselectivies.

Investigation of Intermolecular C-H···Halogen Hydrogen Bonded Supramolecular Assemblies in Three Copper(Ⅰ) Complexes Formed by 3,3'-Dimethoxy-6,6'-dimethyl-2,2'-bipyridine Ligand

Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.

Synthesis, Crystal Structure and Fluorescene of a One-dimensional Compound {CdI_2(2,2′-bipy)}_n

The title compound, {CdI2（2,2＇-bipy）}n, was prepared by the hydrothermal reaction of CdI2 and 2,2＇-bipy in an aqueous solution, and its crystal structure was determined by X-ray single-crystal analysis. Crystallographic data for 1： C10H8N2CdI2, monoclinic system, space group C2/c, a = 16.927（1）, b = 10.0925（7）, c = 7.7422（3） A, β = 106.0629（4）°, V = 1271.00（14） A^3, Z = 4, F（000） = 944,/a = 6.546 mm^-1, Dc= 2.730 g/cm^3, Mr = 522.38, the final R = 0.0309 and wR = 0.0805 for 1310 observed reflections （I 〉 20（I））. X-ray crystal structure analysis shows that the Cd atom is coordinated by four iodines and two N atoms from one 2,2＇-bipy to form an 1-D chain-like structure through bridging iodines. The fluorescene of the title compound was also discussed.

Syntheses and Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)_2Cl]·ClO_4 and [Zn(bipy)_2Cl]·BF_4

Two new transition metal complexes, [Ni（bipy）2Cl]·ClO4 （bipy = 2,2＇-bipyridine） 1 and [Zn（bipy）2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776（1）, b = 12.067（1）, c = 16.146（2）A, β = 93.021（2）o, V = 2031.9（4） A^3, Mr = 505.98, Dc = 1.654 g/cm^3, μ = 1.255 mm^–1, F（000） = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with Ⅰ 〉 2σ（Ⅰ）. For 2, a = 10.758（4）, b = 12.058（4）, c = 16.135（5） A, β = 104.57（1）o, V = 2025.7（12） A^3, Mr = 500.00, Dc = 1.639 g/cm^3, μ = 1.396 mm^–1, F（000） = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen-sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy ···anion···bipy- M hydrogen bonding interactions between the chelating ligands of bipy and anion.

A Three-dimensional Supramolecular Complex {[Co(H_2btec)(2,2'-bipy)(H_2O)_3]·H_2O}_n Assembled via Hydrogen Bonding and π-π Stacking Interactions

A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffraction,elemental analysis,IR and X-ray powder diffraction.The crystal belongs to the triclinic system,space group P1,with a=7.230（3）,b=11.626（5）,c=14.001（6）,α=108.12（0）°,β=95.85（0）°,V=1095.33（157）3,C20H20CoN2O12,Mr=539.31,Z= 2,Dc=1.635 g/cm3,μ=0.855 mm-1,F（000）=554,R=0.0427 and wR=0.1042 for 3883 observed reflections （I 〉 2σ（I））.The title compound features a discrete molecular structure,which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network.Additionally,two different patterns of π-π stacking interactions further consolidate the framework.

Synthesis and Structural Characterization of Gd(Ⅱ ) Coordination Polymer [Gd_2(μ-phth)_3(b-pd)(H_2O)_5]_n

A new Gd（Ⅱ） complex [Gd2（μ-phth）3（b-pd）（H2O）5], （phth = o-phthalato, b-pd = N,Nbipyridine） has been ＇synthesized by the reaction of GdO2 with o-phthalate, H2O and 2,2＇-bipyridine. The crystal structure has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 11.82920（10）, b = 13.53550（10）, c = 13.7381（2）A^°, α= 88.99,β= 66.9120（10）, γ = 66.2370（10）°, V = 1826.02（3） ,A^°3, Dc= 1.915 g/cm^3, C34H30N2O17Gd2, Mr= 1053.10, F（000） = 1024,μ = 3.680 mm^-1, Z = 2, R = 0.0612 and wR = 0.1320 for 6259 observed reflections （I〉 2σ（I））. In the title complex, the Gd（Ⅱ） ions are bridged by o-phthalate ligands in a bidentate mode, producing a 1D infinite chain structure. Each eight-coordinated Gd（Ⅱ） center is coordinated by eight oxygen atoms from phth to give a distorted dodecahedral geometry, and each nine-coordinated Gd（Ⅱ） center is coordinated by two N atoms from b-pd and seven oxygen atoms from phth to give a distorted geometry of capped square antiprism. The chains are linked by π-π interactions and hydrogen bonds between oxygen atoms of carboxylate groups and H2O molecules and hydrogen atoms of H2O, b-pd and o-phth molecules, forming an unusual three-dimensional coordination polymer.

Synthesis,Crystal Structure and Characterization of a New Mixed-valence Cu(Ⅰ)/Cu(Ⅱ) Complex [Cu(bipy)(Me_2dtc)CuI_2]_n

A new one-dimensional mixed-valence Cu（Ⅰ）/Cu（Ⅱ） complex [Cu（bipy）（Me2dtc）CuI2]n 1 （bipy = 2,2′-bipyridine and Me2dtc = N,N-dimethyldithiocarbamate） has been synthesized under solution condition, and characterized by elemental analysis, IR spectrum, single-crystal X-ray diffraction and magnetic property. The crystal belongs to the tetragonal system, space group P4122 with a = b = 11.6504（16）, c = 13.466（3） A, V = 1827.8（5） A^3, Z = 4, Dc = 2.389 g/cm^3, Mr = 657.27, λ（MoKa） = 0.71073 , μ = 5.931 mm·1, F（000） = 1236, the final R = 0.0483 and wR = 0.1245. A total of 2102 unique reflections were collected, of which 2009 with I 〉 2σ（I） were observed. 1 consists of polymeric [Cu^II2]nn^- anions and [Cu^II（bipy）（Me2dtc）]^＋ cations. It is interesting that the cations of 1 interact through π-π stacking interactions after rotating 90° to form one-dimensional chains parallel to the anion chains. The magnetic study indicates antiferromagnetic behavior for this complex.

[Cu(2,2'-bpy)Cl_2]和[Cu(1,10-phen)Cl_2]在多金属氧酸盐上的多相化:选择性氧化四氢化萘的新催化剂(英文)

Mononuclear Cu(II)bipyridine(1)and phenantroline complexes(2)were synthesized and immobilized by different procedures on H3PW12O40 polyoxometalate(POM).Characterization by XRD and SEM-EDX were performed to assess the preservation of the Keggin structure and stoichiometry of the complex.The immobilized complexes were tested as heterogeneous catalysts for the partial oxidation of tetralin(1,2,3,4-tetrahydronaphthalene)using hydrogen peroxide as oxidant in acetonitrile/water as solvent.[Cu(2,2'-bpy)Cl][H2PW12O40] and[Cu(1,10-phen)Cl][H2PW12O40]oxidized tetralin at room temperature,with 16%conversion with(2),to 1-tetralone and 2-tetralone with 83%selectivity.However,the selectivity for 1-tetralone was only 56%.Different preparation methods for the heterogenization of these complexes on the POM Keggin unit were compared and used to enhance the selectivity to 1-tetralone to 75%.

Synthesis and Structural Characterization of Bis(2,2'-bpy)bis(azide)cobalt(Ⅲ)nitrate dihydrate

The title complex [CoIII(2, 2?bpy)2(N3)2]種O3?H2O was obtained by an auto-oxidization reaction of cobalt nitrate with 2, 2-bpy and sodium azide in aqueous solution at room temperature, and violet single crystals were prepared in ethanol solution. The structure was determined by X-ray crystallography. The crystal is of triclinic, space group P ?with a = 8.285(4), b = 11.990(8), c = 12.596(7) ? a = 86.630(3), b = 86.280(5), g = 71.130(10)? C20H20CoN11O5, Mr = 553.40, Z = 2, V = 1180.6(12) ?, F(000) = 568, Dc = 1.557 g/cm3, m = 0.784 mm-1, R = 0.0403 and wR = 0.1008. The title complex consists of a [CoⅢ(2, 2?bpy)2(N3)2]+ cation, a NO3- anion and two lattice water molecules. The center CoⅢ ion coordinated by two chelating 2, 2?bpy ligands and two terminal azide groups with a CoN6 coordination environment exhibits a distorted octahedral geometry.

A Zinc(II) Coordination Polymer Possessing a Linear Trinuclear Building Block [Zn_3(CO_2)_6N_2]

A new coordination polymer [Zn3（bpda）3（bpy）] 1 （H2bpda = 2,2＇-biphenyldicar- boxylic acid, bpy = 4,4＇-bipyridien） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, TG analysis and IR spectrum. 1 Crystallizes in cubic crystal system, space group Ia 3, with a = 20.9687（9） A, V = 9219.7（3） A^3, Z = 8, and R（I 〉 2σ（I）） = 0.0431. Complex 1 is a three-dimensional framework involving a new building block, linear trinuclear {Zn3（CO2）6N2} cluster. In the structure, each bpda coordinates to four zinc atoms via its two bridging bidentate carboxylate groups. To the best of our knowledge, 1 implies a new coordination mode of 2,2＇-biphenyldicarboxylic acid. The solid state fluorescent spectra show a strong emission peak at 451 nm （λex= 341 nm）.

Synthesis and Structural Characterizations of Ternary Iron(Ⅱ)Mixed Ligand Complex:Low Cost Materialsas a Precursor for Preparation of Nanometric Fe_(2)O_(3) Oxide

The reaction of the ligands,ethylenediaminetetraacetic acid terasodium salt(Na 4EDTA)and N—N heterocyclic diamines like2,2’-bipyridine(bipy)with iron(Ⅱ)sulfate with 1∶2∶2 stoichiometric ratios form the mononuclear ternary complex of formulae,[Fe_(2)(EDTA)(bipy)2]at pH~7.The FTIR and Raman laser spectra of the iron(Ⅱ)complex show that 2,2’-bipyridine is present asa bidentate ligand and the ethylenediaminetetraacetic acid terasodium salt as monodentate carboxylate anion.The electronic spectra and magnetic moments data suggest the six coordination number.It has two iron(Ⅱ)centers in octahedral environments,which are interlinked by carboxylato-O atoms of ethylenediaminetetraacetate and by nitrogen atoms of the two 2,2-bipyridine ligands in a chelating mode.Thermal analysis study show thatiron(Ⅱ)complex containing EDTA and 2,2’-bipyridine on its thermalde composition form the corresponding Fe_(2)O_(3) oxide in nano size at the temperature range~475℃.The iron(Ⅱ)complex was performed as a convenient low cost precursor for the preparation of Fe_(2)O_(3) nanoparticles by the the thermal decomposition method.The iron(Ⅲ)oxide composition has been discussedusing FTIR,X-ray diffraction(XRD),transmission electron microscopy(TEM)and energy-dispersive X-ray spectroscopy(EDX).

Synthesis and fluorescence properties of Eu(Ⅲ),Tb(Ⅲ) and Sm(Ⅲ) with β-diketone and 2,2′-bipyridine

Three new rare earth ternary complexes, RE（PPP）3bpy （RE=Sm3＋, Eu3＋, Tb3＋）, were synthesized by the reaction of 1-phenyl-3- （p-phenylethynylphenyl）-1,3-propanedione （HPPP） and 2,2＇-bipyridine（bpy） with rare earth chloride RECl13, respectively, in alcohol solution. The compositions were characterized by means of infrared （IR） spectra, chemical analysis, elemental analysis, and thermodynanaic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm3＋, Eu3＋ and Tb3＋ complexes exhibited characteristic emission of the central ions. The fluorescence spectra showed that the fluorescence emission intensity of Eu3＋ complex was the strongest. The narrow strongest emission band of Eu3＋ complex was considered to be a valuable material with bright red fluorescence.

An efficient synthetic approach towards new 5,5'-diaryl-2,2'-bipyridine-based fluorophores

An efficient approach has been developed for the synthesis of 5,5＇-diaryl-2,2＇-bipyridines via their 1,2,4-triazine analogues.The notable advantages of the present method are：The possibility of varying the aromatic substituents in the positions 5 and 5＇ of bipyridine core and the possibility for obtaining 2,2＇-bipyridines bearing a fused cyclopentene core to increase the solubility in organic solvents.These 5,5＇-diaryl-2,2＇-bipyridines exhibited an intense emission in a range of ca.422-521 nm in acetonitrile solution;depending on the nature of the aromatic substituents and the presence of annulated cyclopentene fragments.Apart from that,the significant bathochromic shifts of the both absorption and emission maxima were observed in comparison with a number of previously described similar structures.In some cases the significant increasing of the fluorescence quantum yields took place.

Preparation of luminescent polystyrene microspheres via surface-modified route with rare earth(Eu^(3+) and Tb^(3+))complexes linked to 2,2'-bipyridine

Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope(TEM), scanning electron microscope(SEM), energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FT-IR), and fluorescence spectrophotometer, were used to characterize the resultant polystyrene composite microspheres. This work highlights the idea that it is facile to synthesis luminescent microspheres by surface-modified method directly.

Two Cd(Ⅱ)-biphenyl-3,3’-disulfonyl-4,4’-dicarboxylate-2,2’-bipyridine Compounds: Structures and Luminescence

Two coordination polymers based on the mixed ligands of biphenyl-3,3?-disul-fonyl-4,4?-dicarboxylate(BPDSDC4–)and 2,2?-bipyridine(2,2?-bpy),{[Cd(BPDSDC)0.5(2,2?-bpy)(H2O)]·(H2O)}n(1)and{[Cd(BPDSDC)0.5(2,2?-bpy)2]·(H2O)}n(2)were synthesized.Both compounds crystallize in the monoclinic system,space group P21/n.For 1,a=7.5737(2),b=17.4284(5),c=13.5982(5)?,β=90.788(3)°,V=1794.76(10)?^3,Z=4,C17H15N2O7SCd,Mr=503.77,Dc=1.864 g/cm^3,μ=1.378 mm^?1,F(000)=1004,the final R=0.0299 and wR=0.0644 for 3137 observed reflections with I>2s(I).For 2,a=13.3097(2),b=10.66240(10),c=17.6583(3)?,β=91.779(2)°,V=2504.74(6)?^3,Z=4,C27H21N4O6SCd,Mr=641.94,Dc=1.702 g/cm^3,μ=1.008 mm^?1,F(000)=1292,the final R=0.0244 and wR=0.0583 for 4594 observed reflections with I>2s(I).The Cd(II)atoms in both compounds are six-coordinated.In 1,the Cd(2,2?-bpy)units are connected by BPDSDC4–ligands to generate a one-dimensional(1D)ribbon structure.The 1D ribbons are linked by the hydrogen bonds and π···π interactions to give a three-dimensional(3D)structure.In compound 2,the Cd(2,2?-bpy)2 units are linked by the BPDSDC^4–ligands to form a 1D chain.Compounds 1 and 2 show luminescent emissions.

Study of the Ion Channel Behavior of Didodecyldimethylammonium Bromide Formed Bilayer Lipid Membrane Stimulated by PF_6^-

Bilayer lipid membranes (BLM) formed from didodecyldimethylammonium bromide were made on the freshly exposed surface of a glassy carbon (GC) and were demonstrated by the ac impedance spectroscopy. The ion channels of membrane properties induced by PF -_6 were studied by the cyclic voltammetric methods. Experimental results indicated that the ion channel of BLM was open in the presence of the PF -_6 due to the interaction of PF -_6 with the BLM, while it was switched off in the absence of PF -_6. Because the ion channel behavior was affected by the concentration of PF -_6, a sensor for PF -_6 can be developed.