Syntheses and Structures of Two Ruthenium(III)Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh_3)_3Cl_2] with tetraethylthiuram disulfide[Et_2NCS_2]_2 or tetra-iso-pmpylthiumm disulfide[~iPr_2NCS_2]_2 afforded mthenium(Ⅲ)complexes[Ru(PPh_3)_2(S_2CNR_2)cl_2]·CH2Cl2(R=Et 1,~iPr 2)which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group Pīwith a=11.5065(6),b=12.1458(7),C=18.0034(9)(A),α=109.380(4),β=95.279(4),γ=97.969(4)°,ν=2324.8(2)(A)~3 and Z=2.Complex 2 belongs to the monoclinic system,space group P21/n with a=12.5752(3),b=20.7562(5),e=17.6821(3)(A),β=105.934(1)°,ν=4437.94(17)(A)~3 and Z=4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh_3 ligands in mutually tram and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2)and 2.369(2)(A) for 1,and 2.376(2),2.414(1)and 2.383(2)(A) for 2,respectively.The electrochemical properties of these two complexes were studied in CH_2Cl_2 solution by cyclic voltammetry.     

Synthesis and Crystal Structure of {(PPh3)2ClRu(μ-Cl)-Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O)

The title compound has been synthesized by the reaction of [RuCl2(PPh3)3] and closo-[B10H10]2- in (CH3)2CHOH solution. Crystals suitable for a single crystal X-ray diffraction analysis were obtained from n-pentane diffused to CH2Cl2 solution. The crystal {(PPh3)2ClRu(μ-Cl)Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O) is monoclinic , space group P21/n , Mr=1359.47, with a=19.434(4), b =14.340(4), c=25.865(9)(A), β= 95.48(3)°, V=7175(4)(A)3, Dc=1.258 g/cm3, Z=4, λ(MoKα)=0.71073(A),μ=6.03 cm-1, F(000)=2784, R=0.0631, wR2= 0.1425, S=1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh3)RuB10H7[OCH(CH3)2]3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.     

Two Amine-tethered Imidazolium NHC Ni(Ⅱ) Complexes: Synthesis,Structure and Catalytic Activity

Nickel(Ⅱ) complexes Ni(L1)2(1) and Ni(L2)2·CH3CN·H2O(2)(L1Cl = 2-(3-benzyl-2,3-dihydroimidazlo-1-yl)-N-(pyridin-2-yl)acetamide, chloride salt, L2Cl = 2-(3-naphthalene-2-ylmethyl)-2,3-dihydro-imidazlo-1-yl)-N-phenylacetamide, chloride salt) with amide-functionalized imidazolium NHC ligand were synthesized and determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 9.2561(19), b = 15.138(3), c = 20.750(4) , β = 90.216(3)°, V = 2907.3(10) 3 and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Pbca with a = 15.5469(16), b = 15.3521(15), c = 31.177(3) , V = 7441.2(13) 3 and Z = 8. They are stable in the air and formed via intermolecular weak interactions, including C–H···π contacts and C–H···O hydrogen bonds. Complex 1 was applied in Suzuki coupling reaction through the investigation of reaction conditions under the optimal choice conditions: 80 ℃, K3PO4, 3% mol catalysts, 6% mol PPh3 and toluene as solvent system could afford 96% yield in 5 h.     

Synthesis, DNA-binding and photocleavage studies of ruthenium(Ⅱ) complexes [Ru(btz)_3]~(2+) and [Ru(btz)(dppz)_2]~(2+)

Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm,...     

Synthesis and Structure of a Zinc(II) Complex:[Zn(Pybta)·Cl_2]_n

The title compound, [Zn(Pybta)Cl2]n (Pybta = 1-(2-pyridylmethyl)benzontriazole), has a zigzag chain structure. It crystallizes in the monoclinic system, space group P21/c with a = 9.0103(11), b = 17.0276(18), c = 9.2288(11) , β = 101.309(6)o, Mr = 346.51, V = 1388.4(3) 3, Z = 4, Dc = 1.658 g/cm3, F(000) = 696, μ = 2.143 mm1, the final R = 0.0492 and wR = 0.1236 for 2545 observed reflections with I > 2σ(I). The Zn atom is four-coordinated by two N and two Cl atoms, forming a slightly distorted tetrahedral geometry. Each zigzag chain links its adjacent symmetry- related equivalents via multiple π-π interactions, which are not frequently observed in the previously reported architectures.     

Syntheses and Crystal Structures of Two Heterobimetallic Clusters [WOS_3Cu_3I(dmpzm)_2]·2(MeCN)_(0.5) and [WS_4Cu_4I_2(dmpzm)_2]·DMF(dmpzm=Bis(3,5-dimethylpyrazolyl)methane)

The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I(dmpzm)2]·2(MeCN)0.5(1·2(MeCN)0.5) while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2(dmpzm)2]·DMF(2·DMF).Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2(MeCN)0.5 crystallizes in triclinic,space group P1-with a = 11.4552(5),b = 11.6735(3),c = 16.2278(9) ,α = 99.537(9),β = 101.986(2),γ = 118.464(13)o,V = 1775.5(3)3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193(2) K,C24H35Cu3IN9OS3W,Mr = 1063.22,F(000) = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145(4),b = 11.464(2),c = 7.7370(15) ,V = 1964.2(6)3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193(2) K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F(000) = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2(MeCN)0.5 consists of one CuI and two [Cu(dmpzm)]+ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.     

环戊二烯基钌配合物催化的高选择性苯乙炔二聚反应

Transition metal vinylidene complexes (M=C=CHR) have attracted a great deal of attention in recent years as a new type of organometallic intermediates that may have unusual reactivity[1]. Their reactivity has been explored and their application to organic synthesis is developed[2]. Recent reports on the ruthenium-vinylidene complexes[3]suggest that the reaction of ruthenium-vinylidene complexes with a base generates the coordinatively unsaturated ruthenium acetylide species, which are involved in a number of catalytic and stoichiometric reactions of alkynes. For example,the coordinatively unsaturated ruthenium acetylide species C5Me5Ru(PPh3)-C≡CPh,formed from the reaction of the vinylidene complex C5Me5Ru(PPh3) (Cl)=C=CHPh with a base was reactive toward a variety of small molecules and active in catalytic dimerization of terminal alkynes[4]. The dimerization of terminal alkyne is an effective method of forming enynes, but its synthetic application in organic synthesis has been limited dueto low selectivity for dimeric products[5]. In this communication, we report that three ruthenium complexes were used as catalysts for the highly selective dimerization of phenylacetylene.     

Construction and Photoluminescence Properties of Zn(Ⅱ)/Cd(Ⅱ) Complexes with 4-Amino-3,5-propyl-1,2,4-triazole Ligand

Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole(dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4](I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4](Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a = 11.865(2), b = 14.464(3), c = 15.985(3) , V = 2743.4(9) 3, Z = 4, C16H32N8Cl4Zn2, Mr = 609.4, Dc = 1.475 g·cm3, μ = 2.16 mm-1, F(000) = 1248, GOOF = 1.091, the final R = 0.0295 and wR = 0.0665 for 1999 observed reflections(I 2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a = 11.408(2), b = 15.211(3), c = 18.152(6) , β = 123.75(2)o, V = 2619.1(1) 3, Z = 2, C32H64N22Cl4Cd3, Mr = 1236.05, Dc = 1.567 g·cm3, μ = 1.46 mm-1, F(000) = 1244, GOOF = 1.042, the final R = 0.0444 and wR = 0.0913 for 3466 observed reflections(I 2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids(τ = 0.34). The hydrogen bonds of C–H···Cl and N–H···Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.     

SYNTHESIS AND STRUCTURE OF trans-RuCPh_2PN(i-Bu)PPh_2]_2Cl_2

<正> The reaction of Ru(DMSO)4Cl2 and Ph2PN (i-Bu)Ph2(1:2) gave the title compound, trans-RuCPh2PN(i-Bu)PPh2]2Cl2. Crystallographic data for C56 H58Cl2N2P4Ru: triclinic, space group P1, a = 11. 575(1), b = 12. 193(3), c = 20. 297(4)A, α=75. 30(2),β=76.28(1),γ= 72. 08(2)°, V = 2596. 6(8)A3, Z = 2, Mr = 1054. 97, Dc=1. 35g/cm3,μ(MoKa) = 5. 58cm-1, F (000) = 1092; R = 0. 046 and Rw = 0. 056 for 3411 observed reflections. The Ru atom is coordinated by four P atoms and two Cl atoms, forming an octahedral configuration.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Syntheses and Characterizations of Cd(Ⅱ) and Pr(Ⅲ) Complexes Based on 5-(Tetrazol-5-yl) Isophthalic Acid

Hydrothermal reactions of 5-(tetrazol-5-yl) isophthalic acid with cadmium nitrate/praseodymium nitrate led to two complexes of [Cd_3(TZI)_2(H2_O)_(11)]_n(1) and [Pr(TZI)(H_2O)_5]_n(2). Their structures and properties were determined by X-ray diffraction, IR spectroscopy, fluorescence spectrum, thermal gravimetric analyses and elemental analysis. Complex 1 belongs to monoclinic system, I2/c space group, with a = 12.8688(3), b = 18.0925(3), c = 14.5190(3) ?, β = 116.054(3)°, V =3036.92(13) ?~3, Z = 4; complex 2 crystallizes in triclinic, space group P 1, with a = 7.9690(5), b =9.7665(8), c = 10.4353(9) ?, α = 116.709(9), β = 107.461(6), γ = 95.671(6)°, V = 665.54(9) ?3 and Z =2. Complex 1 is a 3D planar structure. Complex 2 is a one-dimensional double chain configuration and extends into a 3D network by hydrogen bonds and π-π interactions.     

Synthesis and Structure of a Ruthenium（Ⅱ）-dithiocarbamate Complex [RuH（CO）（PPh_3）_2（4-ClPhNHCS_2）]·C_6H_（14）

The title complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)]·C6H14 has been prepared and characterized by X-ray diffraction analysis.It crystallizes in the triclinic system,space group P1 with a = 11.0817(2),b = 14.3889(2),c = 15.2136(2) ,α = 71.018(1),β = 74.911(1),γ = 85.146(1)°,V = 2214.86(6) 3,Z = 2,Mr = 900.4,Dc = 1.350 g/cm3,Mr = 900.40,μ(MoKα) = 0.616 mm-1,F(000) = 926,S = 1.016,the final R = 0.0478 and wR = 0.0947 for 6828 observed reflections with I > 2σ(I) and 505 variables.The molecular structure of 1 consists of one neutral complex [RuH(CO)(PPh3)2(4-ClPhNHCS2)] and one hexane solvent molecule.The geometry around ruthenium is pseudo-octahedral with two trans-binding PPh3 ligands and one chelating bidentate 4-ClPhNHCS2- ligand via two sulfur atoms.The average Ru-S,Ru-P and Ru-H bond lengths are 2.4824(8),2.3495(8) and 1.71(2),respectively.The electrochemical properties of 1 have been studied in CH2Cl2 solution by cyclic voltammetry.     

Synthesis, Structure and Luminescent Properties of Polymeric Copper（Ⅰ） Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper(I) halide complexes bearing phosphine and N-donor bridging ligands,[(PPh3)2Cu2(μ-Br)2(μ-4,4′-bipy)]∞ 1 (bipy=bipyridine),[(PPh3)2Cu2(μ-Br)2(μ-bpe)]∞ 2 (bpe=trans-1,2-bis(4-pyridyl)ethene) and [(PPh3)2Cu2(μ-Cl)2(μ-bpe)]∞ 3,were synthe-sized by the multilayer diffusion method,and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic,space group P1 with a=9.122(3),b=9.322(3),c=13.201(4),α=106.440(4),β=105.965(5),γ=94.167(5)°,V=1021.3(6) 3,Mr=967.62,Z=1,Dc=1.573 g/cm3,F(000)=486,μ=3.111 mm-1,the final R=0.0383 and wR=0.0960 for 2792 observed reflections (I > 2σ(I)). Complex 2 crystallizes in triclinic,space group P1 with a=9.420(3),b=10.209(4),c=12.407(4),α=104.136(6),β=108.132(5),γ=95.338(6)°,V=1081.0(7) 3,Mr=496.83,Z=2,Dc=1.526 g/cm3,F(000)=500,μ=2.941 mm-1,the final R= 0.0445 and wR=0.1117 for 3251 observed reflections (I > 2σ(I)). Complex 3 crystallizes in triclinic,space group P1 with a=8.32(1),b=11.53(2),c=13.94(3),α=109.57(3),β=93.85(3),γ= 97.28(3)°,V=1242(4) 3,Mr=1074.59,Z=1,Dc=1.436 g/cm3,F(000)=548,μ=1.279 mm-1,the final R=0.0786 and wR=0.1586 for 2266 observed reflections (I > 2σ(I)). The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand (IL) and metal-to-ligand charge-transfer (MLCT) excited state.     

Synthesis and Structure Characterization of a Tetranuclear Manganese(Ⅲ) Complex:[Mn_4O_2(O_2CMe)_6(MeOH)_2(dbm)_2]·2MeCOOH·2CH_2Cl_2

The title compound, [Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2 (Hdbm = dibenzoylmethane), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1, with a = 10.729(3), b = 12.269(3), c = 13.085(4) , α = 106.367(3), β = 107.643(2), γ = 94.771(2)o, V = 1547.9(7) 3, Z = 1, C50H64Cl4Mn4O24, Mr = 1410.57, Dc = 1.513 g/cm3, F(000) = 724, Rint = 0.0147, T = 293(2) K and μ = 1.046 mm–1. The final R = 0.0359 and wR = 0.0938 for 5791 observed reflections with I > 2σ(I). The structure of the complex consists of one [Mn4(μ3-O)2]8+ core with four coplanar Mn atoms disposed in an extended “butterfly-like” arrangement and two O atoms triply bridging each “wing”, and the peripheral ligation is provided by six μ2-MeCO2– , two terminal μ2-dbm– groups at the two ends of the molecule, and two MeOH molecules on the central Mn atoms. Intermolecular O…H–O hydrogen bonding interactions are found within the structure of the compound.     

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates:[Cu~Ⅱ_2(HL)_3]_2[Mo_8O_(26)]·(H_2O)_4 and [Ni~Ⅱ(HL)_3]_2(Mo_8O_(26))·(H_2O)_3(HL=3-(2-Pyridyl)pyrazole)

Two new polyoxomolybdate compounds,namely CuII2(HL)3]2[Mo8O26]·(H2O)4(1) and [NiII(HL)3]2(Mo8O26)·(H2O)3(2)(HL = 3-(2-pyridyl)pyrazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu(II) ions linked by three 3-(2-pyridyl)pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-(2-pyridyl)pyrazole ligands.Crystal data of 1:C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850(2),b = 18.510(4),c = 17.230(3) ,β = 100.57(3)°,V = 3401.6(12) 3,Z = 4,Dc = 2.324 g/cm3,F(000) = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775(Ⅰ 2σ(Ⅰ));Crystal data for 2:C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799(2),b = 14.7970(13),c = 23.141(2) ,β = 91.6180(10)°,V = 7119.0(11) 3,Z = 4,Dc = 2.077 g/cm3,F(000) = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696(Ⅰ 2σ(Ⅰ)).     

Vanadium(Ⅳ)dimer complexes containing [V(o-C_6H_4OS)_3]~(2-)fragment and caged sodium ions

Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A=Ph_4P~+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared bythe reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N~+,L=L'=MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com-plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti-bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space groupP1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V=2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono-clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8,and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)3]~(2-) fragmentslinked by sodium ions through the μ_3-O bridges with a crystallographic center of symmetry.The V(IV)atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.     

A series of novel Zn(Ⅱ) and Mn(Ⅱ) metal-organic frameworks constructed by 2,4-bis-oxyacetate-benzoic acid: syntheses,structures and photoluminescence

A new carboxylic acid ligand, 2,4-bis-oxyacetate-benzoic acid(H3BOABA), was designed and introduced to construct novel metal-organic framework materials. [Zn Na(BOABA)(phen)(H2O)]·H2O(1), Zn Na(BOABA)(2), Mn3(BOABA)2(phen)2(3), [Mn2(BOABA)(OH)]·(H2O)2(4)(CCDC: 885138, 885137, 894225, 883094) were hydrothermally synthesized and characterized by elemental analysis, IR spectra and thermal gravimetric analyses. Crystal structures of the complexes were determined by single crystal X-ray diffraction method. Complex 1 is a one dimensional double edges non-interpenetrated framework decorated by the phen ligands on the surface. Complex 2 is an unique three dimensional open framework, consisting of Zn(II) and Na(I). Complex 3 is an unique double edges one dimensional MOF containing a [Mn3(BOABA)2(phen)2]n non-interpenetrated structure. Complex 4 is a two dimensional plane structure containing two Mn atoms in the same coordination environment. The interaction between four complexes and DNA were studied by Et Br fluorescence probe. Meanwhile, photoluminescence studies revealed that these four complexes display strong fluorescent emission bands in the solid state at room temperature.     

Synthesis,Crystal Structure and Spectroscopy Studies on Complex cis-Os~Ⅱ(bpy)_2Cl_2 and Its Oxidation Product [cis-Os~Ⅲ(bpy)_2Cl_2](PF_6)

The treatment of(NH_4)_2 OsCl_6 with 2 equiv of bpy in ethylene glycol produced complex 1, cis-Os~Ⅱ(bpy)_2Cl_2(bpy = 2,2?-bipyridine). Its one-electron oxidation product 2, [cis-Os~Ⅲ-(bpy)_2Cl_2](PF_6), was obtained by the oxidation of 1 with(Cp)_2 FePF_6. Complex 1 crystallizes in the orthorhombic space group Pbca, and adopts distorted [MCl_2 N_4] octahedral coordination, in which four coordination sites are occupied by four nitrogen atoms from two bpy ligands and the other two sites are occupied by two chlorine atoms in a cis-position. Complex 2 crystallizes in monoclinic space group C2/c, and contains one [Os(bpy)_2Cl_2]~+ cation, one PF_6~- anion and two uncoordinated water solvent molecules.     

Synthesis of New Ruthenium（Ⅱ）Bipyridyl Complexes and Studies on Their Photophysical and Photoelectrochemical Properties

Two new mixed-ligand ruthenium(Ⅱ） complexes,Ru(dcbpy)-(LL)NCS)2[where dcbpy=4,4‘-dicarboxyl-2,2‘‘-bipyridine,LL=4,4‘-bis(N-methyl-anilinomethyl)-2,2‘‘-bipyridine(2)],were synthesized,and the tphotophysical properties of these complexes were studied.The metal-to-ligand charge transfer (MLCT) transitions of these complexes exhibited solvatochromic effect due to the existence of NCS ligands.The MLCT energies also strongly depend on the pH values of the solutions because of protonation and deprotonation of the carboxyl groups.The pKa values of the ground state,4.0 for 1 and 3.8 for 2,were obtained from the titration curves.The photoelectrochemical properties of 1 and 2 as sensitizers in sandwich-type solar cells have been studied.Complex 1 exhibited better photoelectrochemical behavior than complex 2 as expected.It was proved that the design of mixed-ligand complex by introducing electron donating group in one of the ligands should be a promising approach.     

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex [Cu(C_(13)H_9N_2O)Cl]_2·(CH_3CN)_2 with Ligand 2-Benzimidazol

A new dinuclear copper complex, [Cu(C13H9N2O)Cl]2·(CH3CN)2 (C30H24Cl2Cu2N6O2), has been synthesized and characterized by X-ray structure determination. It crystallizes in the tricli- nic system, space group P1, with a = 7.6677(14), b = 9.2375(17), c = 11.227(2) , α = 81.338(3), β = 88.173(4), γ = 66.199(3)o, V = 718.9(2) 3, Z = 1, Mr = 698.53, F(000) = 354, Dc = 1.613 g/cm3, μ(MoKα) = 1.705 mm-1, the final R = 0.0645 and wR = 0.1364 for 2474 unique reflections with 1809 observed ones (I > 2σ(I)). In the title complex, each copper(II) atom is located at the center of a distorted tetrahedron consisting of four coordinate atoms (one nitrogen atom, two oxygen anions, and one chlorine atom). Two copper(II) atoms are bridged by two oxygen anions (O(1) and O(1a)) of two phenolates to form a Cu(II)–Cu(II) binuclear entity, and the distance between two copper(II) atoms is 3.0144(15) .