Synthesis,Structure and Properties of a Novel Infinite Triple Helices Coordination Polymer{[Co(4,4'-bipyridine)(4,4'azobispyridine)_(2)(NCS)_(2)]·H_(2)O}_(n)

The novel complex{[Co(bipy)(azpy)_(2)(NCS)_(2)]·H_(2)O}n(where bipy=4,4′bipyridine,azpy=4,4′azobisp yridine)has been synthesized and characterized by elemental analyses,IR,UV,thermal analyses,and variable temperature magnetic susceptibility.The crystal(C_(32)H_(26)CoN_(12)OS_(2),Mr=717.70)belongs to the orthorhombic,space group Pnna,a=2.21312(16)nm,b=1.40403(10)nm,c=1.14237(8)nm,V=3.5497(4)nm^(3),Z=4,Dc=1.343g·cm^(-3),μ=0.645mm^(-1),F(000)=1476,and final R_(1)=0.0691,wR_(2)=0.1129 for 231 parameters and 1674 observed reflections[I>2.00σ(I)].The Co(Ⅱ)atom is,in a distorted octahedral geometry,coordinated by six nitrogen atoms from two bridging bipy,two monodentate azpy,and two thiocyanate groups.The bridging ligand bipy links Co(Ⅱ)atoms to form the infinite“rod"with terminal coordination azpy ligand acting as sidearms.Unprecedented three parallel interpenetrating two dimensional(4,4)networks and novel infinite triple helices are formed via hydrogen bonding interactions.CCDC:155588.

Synthesis and Structure of an Interlock Network Frame of Cobalt(Ⅱ) Coordination Polymer {[Co(azpy)_2(NCS)_2]·1/4EtOH·1/2H_2O}_n (azpy=4,4′-Azobispyridine)

A compound {[Co(azpy)2(NCS)2]·1/4EtOH·1/2H2O}n(1), where azpy=4,4’-azobispyridine, was synthesized and characterized by means of IR, TGA-DTA, magnetic susceptibility and X-ray single crystal diffraction. It consists of two independent sets of fully interlocked two-dimensional networks with the dihedral angle 61.7°, organized in parallel stacks of the sheets which are made of edge-shared [Co(Ⅱ)]4squares separated by 0. 9062nm, and defined size rhombic channels. The thermal gravimetric analysis indicates that the framework is stable up to 198℃. The variable-temperature magnetic susceptibility measurements indicated that there is a weak antiferromagnetic interaction between the cobalt(Ⅰ) ions in the complex (1).

Construction and the Second-order Nonlinear Optics of a New Chiral Coordination Network Based on Two Types of Homo-chiral Helices

A new 2D chiral cadmium coordination network [Cd（TCBA）2]？2EtOH （1） was prepared by the reaction of achiral angular asymmetric bridging ligand 2-（（3,5-dimethyl- 4H-1,2,4-triazol-4-yl）-carbamoyl）-benzoic acid （TCBA） with cadmium acetate, which was structurally characterized by IR, elemental analysis, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 crystallizes in the chiral space group P21 and features a 2D chiral network consisting of two types of homo-chiral helices, which are further extended into a 3D chiral framework along the a-axis via hydrogen bonds. Moreover, powder second-order nonlinear optical （NLO） measurements reveal complex 1 has a modest second-harmonic-generation （SHG） efficiency at room temperature.

Crystal Structure and Antitumor Activity of Tri[2- [N-(4'-methyl-benzylsulfonyl)amino]ethyl]-amine

The crystal structure of the title compound (C27H38N4O7S3, Mr = 626.79) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pīwith a = 9.411(1), b = 11.645(2), c = 14.672(2) , a = 91.80(1), b = 95.36(1), g =104.56(1)o, V = 1547.0 3, Z = 2, Dc = 1.346 g/cm3, l = 0.71073 , m(MoKa) = 0.289 mm-1 and F(000) = 664. The structure was refined to R = 0.0406 and wR = 0.1177 for 4103 observed reflections with I > 2s(I). X-ray diffraction analysis reveals that the title compound is a practically distorted tetrahedron and each molecule contains one lattice H2O by hydrogen bond. The antitumor activity of the title compound against HL-60 human leukemia cells has also been studied by MTT method.

Synthesis and Crystal Structure of {[Mn(H_2O)_4(3,3'-?azpy)](3, 3'-azpy)_3(PF_6)_2}_n

The complex {[Mn(H2O)4(3, 3?azpy)](3, 3?azpy)3(PF6)2}n (3, 3?azpy = 3, 3? azobispyridine) has been synthesized and characterized. The crystal (C40H40F12MnN16O4P2, Mr = 1153.76) belongs to the triclinic system, space group P with the following crystallographic parameters: a = 10.761(2), b = 11.040(2), c = 23.365(4) ? a = 85.52(1), b = 82.69(1), g = 70.44(1)? V = 2592.5(8) 3, Dc = 1.478 g/cm3, m(MoKa) = 4.16 cm-1, F(000) = 1174, Z = 2, final R = 0.0493 and wR = 0.1158 for the observed reflections (I > 2.00s(I)). The X-ray analysis revealed that manganese(Ⅱ) cation coordination environment is a distorted octahedral geometry, and the Mn2+ cation is coordinated by four oxygen atoms of water in the equatorial plane, while the two nitrogen atoms of 3, 3?azpy occupy the axial positions. The complex forms a one-dimensional chain structure via 3, 3?azpy bridging ligand.

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver(I) Cluster

A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in monoclinic, space group P21/c with a = 16.101（4）, b = 24.855（7）, c = 14.492（4） A, β = 109.730（5）, V = 5459（3） A3, C90H102Ag6N2406S6, Mr= 2455.54, Dc= 1.494 g/cm3,μ（MoKa） = 1.228 mm^-1, F（000） = 2472, Z = 2, the final R = 0.0761 and wR = 0.1507 for 5258 observed reflections （I〉 2α（I））. In the structure, the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag6L6 cluster. Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.

Synthesis and Crystal Structure of [2-dapp]_2[Zn(dmit)_2] (2-dapp = 2-(4-Dimethylaminophenyl)ethyl-l-methyl- pyridinium, dmit = 1,3-Dithiole-2-thione-4,5-dithiolato)

The title compound [2-dapp]2[Zn(dmit)2] synthesized by the direct reaction of [Et4N]2[Zn(dmit)2] and [2-dapp]I crystallizes in monoclinic, space group P2l/c with a = 29.7436(6), b = l0.6266(3), c = l3.6161(4) ? b = 93.l16(l)? V = 4297.3 ?, Z = 4, Dc = 1.448 g/cm3, m = 1.091 mm-1 and F(000) = 1936. The structure was refined by fu1l-matrix 1east-squares methods to the final R = 0.075 and wR = 0.l16, revealing the zinc-bis (dmit) anions interact strongly with the planar cation, 2-dapp+, by the hydrogen bond C(l)H(lC)…S(7) (x, 3/2y, 1/2+z).

Synthesis and Crystal Structure of [{Cd(hmbdc)(H_2O)_3}·2H_2O]_n

A novel coordination polymer [{Cd（hmbdc）（H20）3}-2H20],, （hmbdc = 5-hydroxyisophthalic acid） has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2Jc, with a = 9.599（3）, b = 18.699（5）, c = 7.557（2） A, r= 108.198（4）°, V= 1288.6（6） A3, Z= 4, M,.= 382.60, Dc = 1.972 g/cm^, F（000） = 760, p = 1.740, the final R =0.0555 and wR = 0.0995 for 1732 observed reflections with 1 〉 2σ（I）. The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.

Synthesis and Crystal Structure of a Novel Heterometallic Complex [Na_2Cu_2Gd_2(pdc)_4(H_2O)_(14)·2H_2O]

A novel heterometallic complex [Na2Cu2Gd2（pdc）4（H2O）14·2H2O] （H3pdc = 1H- pyrazole-3,5-dicarboxylic acid） has been synthesized and characterized by 1R spectra, elemental analysis, and single-crystal X-ray analysis. The crystal belongs to the monoclinic system, space group P2 1/c with a = 7.9521（18）, b = 12.251（3）, c = 22.293（5） A, β = 110.173（5）°, V= 2038.5（8） A^3, Mr = 1388.13, Z = 2, F（000） = 1352, Dc = 2.261 g/cm^3,/2 = 4.380 mm^-1, the final R = 0.0409 and wR = 0.0622 for 2453 observed reflections with I 〉 2σ（I）. The structural analysis shows that the Na^I, Cu^II and Gd^II ions are linked together by two kinds of bridging ligands （pdc^3- and H2O） to form a main moiety [Na2Cu2Gd2（pdc）4（H2O）14], which can be regarded as a centrosymmetric dimmer of [NaCuGd（pdc）2（H2O）7]. Many hydrogen bonds exist in the complex to build a 3D supramolecular framework.

Synthesis and Crystal Structure of [{Mn(IBG)(2,2'-bipy)(H_2O)}·4H_2O]_n

A novel MnⅡ complex [{Mn（IBG）（2,2＇-bipy）（H2O）}·4H2O]n 1（H2IBG=isophtha-loylbisglycine and 2,2＇-bipy = 2,2＇-bipyridine） has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P21/n,with a=13.667（2）,b=14.045（2）,c=14.195（2）,β=101.483（3）°,V=2670.1（7）3,Z=4,C22H26N4O11Mn,Mr=577.41,Dc=1.436 g/cm3,F（000）=1196.0,μ（MoKα）=0.558 mm-1,the final R=0.0578 and wR=0.1460 for 2974 observed reflections with I2σ（I）.In the structure,the MnⅡ atom is coordinated in a distorted octahedral environment arranged by one water molecule,one 2,2＇-bipy ligand and two IBG ligands.

Structure of Metal Aluminophosphates:Al_(9-x)M_xP_(12)O_(48)(TREN)_4·yNH_4·zH_2O [TREN=N(CH_2CH_2NH_3)H_m,M=Mn,Co]

Two large-pore metal-doped aluminophosphates, Mn4Al5（PO4 ）12[N（ C2H4NH3）3]3 [ N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H=O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H,NH3）3][N（C2H4NH3）2（C2H4NH2）]3· （ NH4 ）4· 13H2O （ Co4-NJU） , which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I（-4）3m with α= 1. 6795（2） nm and V=4. 7374（9） nm^3 for Mn4-NJU, and a=1. 67372（19） nm and V = 4. 6887 （9） nm^3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-（ 2-aminoethyl ）diethylenetriamine （TREN, C6H18N4 ） ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M^2＋ （M = Mn, Co） and Al^3＋ disorderedly occupy the same crystallographic positions.

Synthesis and Crystal Structure of a Cr(Ⅲ) Dimer[Cr_2(8-hqn)_2Cl_4(H_2O)_2]·2(CH_3)_2CO (8-hqn=8-Hydroxyoxyquinolate)

The title complex [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-hydroxyoxyquinolate） has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P^-1 with a = 8.719（1）, b = 9.226（1）, c = 9.717（1） A^°, α = 71.916（2）, β= 78.072（2）, γ = 76.014（2）°, V= 713.72（15） A^°^3, Z= 1, Dc= 1.597g/cm^3, F（000） = 350 and μ（MoKa） = 1.177 mm^-1, the final R = 0.0490 and wR = 0.1055 for 1616 observed reflections with I 〉 2σ（I）. It is a dimer constructed by two monomeric units [Cr（8-hqn）Cl2（H2O）] bridged by phenoxide-like oxygen atom from 8-hydroxyoxyquinolate, where the two six-coordinated Cr（Ⅲ）atoms exhibit an octahedral coordination geometry.

Synthesis and Crystal Structure of 2-Benzoyl Pyridine Thiosemicarbazato Palladium(Ⅱ)Chloride

The title complex, 2 benzoyl pyridine thiosemicarbazato palladium(II) chloride [C 13 H 11 N 4SPdCl, M r =379.17], crystallizes in monoclinic, space group C2/c with a=12.1061(5), b=21.877(3), c=11.4832(6), β=108.29(9)°, V=2887.7(4) 3, Z = 8, D c =1.827g/cm 3; μ= 1.608cm -1 and F(000)=1568. R =0.0281 and wR =0.0684 for 1446 reflections with I>2σ(I) . X ray crystal structure analysis revealed that the coordination geometry of Pd atom is a distorted square plane with two Pd-N bonds, one Pd-S bond and one Pd-Cl bond. The Schiff base ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via the mercapto sulfur and the β nitrogen atoms.

Synthesis and Crystal Structure of [Sm(4-Pyta)_3(H_2O)_2]_n (4-Pyta = 4-Pyridylthioacetate)

A novel coordination polymer [Sm（4-Pyta）3（H2O）2]n has been synthesized by the hydrothermal reaction between 4-Pyta （4-Pyta = 4-pyridylthioacetate） and Sm（NO3）3. The structure was characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space groupP1, with a = 9.100（2）, b = 11.842（3）, c = 12.183（3） A, α= 79.781（4）, β= 74.124（4）, γ = 841882（5）^o, V = 1241.6（5） A^3, Z = 2, Mr = 690.95, Dc = 1.84806 g/cm^3, F（000） = 686,μ = 2.669 mm^-1, the final R = 0.0388 and wR = 0.0808 for 4149 observed reflections with I 〉 2σ（I）. The structural analysis shows that the complex exhibits a one-dimensional architecture. Intermolecular hydrogen bonding interactions are found in the complex molecules.

Synthesis,Crystal Structure and Fluorescence Property of [Y(sip)(H_2O)_4]_n with 5-Sulfoisophthalate Ligand

The title complex, [Y（sip）（H2O）4], （sip = 5-sulfoisophthalate）, has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray analysis. The crystal belongs to the orthorhombic system, space group Pna21, a = 7.235（4）, b = 16.456（5）, c = 10.316（3） A, V = 1228.2（9） A^3, Z = 4, Mr = 404.14, Dc = 2.186 g/cm63, F（000） = 808,μ= 4.979 mm^-1, the final R = 0.0474 and wR = 0.1125 for 2122 observed reflections with I 〉 2σ（I）. The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular structure. The complex shows intense luminescence in solid state at room temperature.

Syntheses and Crystal Structures of Two New Ag(Ⅰ) Complexes with Betaine Derivative: Structure Changes via Metal-to-ligand Ratio

Two new Ag（I） complexes {Ag2（L）（NO3）（H2O）}n（1） and {Ag（L）}n·nH2O（2） have been synthesized via the reaction of silver nitrate and betaine derivative 1-carboxymethylpyridinium-3-carboxylate（L） by only changing the metal-to-ligand ratio. The results of X-ray crystallographic analysis indicate that complexes 1 and 2 both crystallize in the monoclinic space group P21/c with a = 5.0809（14）, b = 17.390（5）, c = 13.399（4）, β = 91.677（5）o, V = 1183.4（6）3, Z = 4, Mr = 475.90, Dc = 2.671 g/cm3, F（000） = 912, μ = 3.352 mm-1, S = 1.259, the final R = 0.0320 and wR = 0.0831 for 2036 observed reflections with I 〉 2σ（I） for 1 and a = 12.180（2）, b = 5.0283（10）, c = 14.396（3）, β = 94.87（3）o, V = 878.5（3）3, Z = 4, Mr = 306.02, Dc = 2.314 g/cm3, F（000） = 600, μ = 2.294 mm-1, S = 1.053, the final R = 0.0283 and wR = 0.0684 for 2011 observed reflections with I 〉 2σ（I） for 2. Complexes 1 and 2 both feature a unique 2D structure. For 1, the 2D undulated network consists of 1D infinite helical chains running parallel to the b axis, while for 2, the 2D network is made up of 1D tubes along the b axis. Moreover, the Ag…Ag interactions in complexes 1 and 2 are 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.

Shape-controlled synthesis and photocatalytic activity of In_2O_3 nanostructures derived from coordination polymer precursors

In（BTC）（phen）（H_2O）nanocrystals with controllable morphology and size were successfully obtained by solvothermal method.Hierarchical straw-sheaf-like architectures,nanorods and elongated hexagons have been synthesized by varying the volume ratio of DMF：H_2O：C_2H_5OH.Phase-pure In_2O_3nanocrystals were obtained by the calcination of the precursors without significant alteration of the morphology.The products were characterized by PXRD,SEM,TEM,TGA,IR and gas adsorption measurements.The photocatalytic effect was investigated for the In_2O_3 nanocrystals with different morphology on the degradation of rhodamine B（Rh B）and it was found that the nanorods exhibited the best photocatalytic activity,which shows the degradation efficiency of 94%for 8 h.The results showed that the photocatalytic activity increased with the increase of BET surface area and pore volume.

Turn-on fluorescence detection of specific inorganic anions by Zr(Ⅳ)-MOF with amino-functional group

Inorganic anions such as phosphates and carbonates are essential in the natural system and it is important for the detec-tion of such species.In this work,the fluorescence sensing capacity of Zr(IV)framework with an amino-functional group,namely UiO-66-NH_(2),towards specific inorganic anions was investigated in aqueous media.The results revealed that the fluorescence emission intensity of UiO-66-NH2 could be strongly enhanced by phosphate and carbonate anions including HPO_(4)^(2-),H_(2)PO_(4)^(-),PO_(4)^(3-),P_(2)O_(7)^(4-),HCO_(3)^(-)and CO_(3)^(2-),implying its sensing capacity towards phosphate and carbonate anions.Furthermore,fluorescence titration experiments exhibit that the emission intensity enhancement ratio depends linearly on the concentration of anions,suggesting the possibility of quantitative detection of these anions.Further studies suggest that the sensing of UiO-66-NH,towards HPO_(4)^(2-)/PO_(4)^(3-)/P_(2)O_(4)^(-)/HCO_(3)^(-)/CO_(2)-could be ascribed to the collapse of the framework,while that for H_(2)PO_(4)-could be attributed to the adsorption of H,PO4-by UiO-66-NH2 with hydrogen bonding interactions between H,PO4-and the amino group of UiO-66-NH_(2) supported by the different fluorescence response of UiO-66 and UiO-66-NH,towards the anions.

Four novel Z-shaped hexanuclear vanadium oxide clusters as efficient heterogeneous catalysts for cycloaddition of CO_(2) and oxidative desulfurization reactions

Chemical fixation of CO_(2)into C1 source, as a general approach, can effectively alleviate the emission of greenhouse gasses. Whereas, the challenge posed by the need for efficient catalysts with high catalytic active sites still exists. In this work, we reported a series of new hexavanadate clusters, [(C6H6ON)2(C2H8N2)2(CH3O)6VIV6O8](V6–1), [(C6H6ON)2(C3H10N2)2(CH3O)6VIV6O8](V6–2), [(C6H6ON)2(C6H14N2)2(CH3O)6VIV6O8](V6–3) and [(C6H6ON)2(C4H11N2O)2(CH3O)4VIV6O8](V6–4), assembled by 2-aminophenol and four different kinds of Lewis bases(LB), ethanediamine(en), 1,2-diaminopropane, 1,2-cyclohexanediamine and N-(2-hydroxyethyl)ethylenediamine(ben) together. Among them, the basic unit {V6} cluster featured Z-shaped configuration represents a brand-new example of hexanuclear vanadium clusters. Remarkably, the catalytic tests demonstrated that V6–1 as catalyst displays high catalytic activity in the cycloaddition for the CO_(2)fixation into cyclic carbonates by virtue of open V sites. As expected, for oxidative desulfurization of sulfides, V6–1 also exhibits satisfied catalytic effectiveness. Furthermore, the recycling test confirmed that catalyst V6–1 may be a bifunctional heterogeneous catalyst with great promise for both CO_(2)cycloaddition and oxidative desulfurization reactions.