Synthesis,Structure and Photophysical Properties of a Dinuclear Copper (Ⅰ) Complex Based on Phosphinopyridine and Diphosphine Mixed-ligands

Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH₃CN)₄BF₄afforded a dinuclear Cu(I)complex[Cu₂(dpppy)₂(dppm)(CH₃CN)](BF₄)₂·3CH₂Cl₂(1).Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail.It crystallizes in triclinic space group P1^-with a=13.0834(8),b=13.5568(8),c=21.8544(11)?,α=76.090(5)°,β=80.803(5)°,γ=64.582(6)°,V=3391.3(3)?³,Z=2,M_r=1507.42,D_c=1.476 g/cm³,F(000)=1532,GOOF=1.071,the final R=0.0700 for 9041 observed reflections with I>2σ(I)and wR=0.2063 for all data.The complex contains a Cu₂-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement.In the crystalline phase,complex 1 exhibits bright bluish-green photoluminescence(λ_max=488 nm)with high quantum yield(?=0.57)at room temperature.It is still a relatively high emission quantum yield(?=0.36)in doped PMMA thin film with 20 wt%dopant of complex 1.The emission peaks of 1 in dichloromethane solution and doped PMMA(20 wt%)thin films are 510 and 494 nm,respectively,showing a very slight bathochromic shift compared to that in crystalline phase.This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.     

Asymmetric transfer hydrogenation of ketones catalyzed by nickel complex with new PNO-type ligands

The new polydentate mixed-N,P,O chiral ligands have been synthesized by the condensation of bis（o-formylphenyl）- phenylphosphane and R-phenylglycinol in CHCl₃,and fully characterized by IR,NMR and EIMS spectra.These ligands were employed with a simple Ni complex Ni（PPh_s）₂Cl₂ in situ as catalytic systems for asymmetric transfer hydrogenation of ketones,and the corresponding optical alcohols were obtained with up to 84%ee under mild conditions.     

Hydrothermal Synthesis,Crystal Structure and Properties of a New Binuclear Nickel(Ⅲ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

A new binuclear nickel(II) complex Ni₂(HPT)_4(H₂O)₃ (1) has been hydrothermally synthesized with nickel hydroxide,3,4-pyridine dicarboxylic acid and 3-(pyridin-2-yl)-1,2,4-triazole (HPT) in the mixed solution (the volume ratio of methanol and water is 1:4).It crystallizes in tetragonal space group P4₂/n,with a=20.844(1),b=20.844(1),c=7.2463(7)A,V=3148.2(5)A³,D_c=1.587 g/cm³,Z=4,μ(Mo Ka)=1.257,F(000)=1544,the final GOOF=1.043,R=0.0437 and w R=0.1297.The crystal structure shows that the whole molecule consists of two nickel ions which are bridged by fourμ₂-η¹:η^0-3-(pyridin-2-yl)-1,2,4-triazole anions.The coordination environment of Ni(II) ion is Ni N₆,giving a distorted octahedral geometry.The thermal stability and fluorescent and magnetic properties of the complex were investigated.     

Spectroscopic study on the interaction between[Hg（SCN）4]2- and hemoglobin

The interaction between[Hg（SCN）₄]^2- and hemoglobin（Hb） under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering（RRS） spectroscopy and circular dichroism（CD） spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg（SCN）₄]^2- and Hb.The possible mechanism suggested for the interaction was that ten Hg（SCN）₄]^2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg（SCN）₄]^2- with Trp was the major cause of the fluorescence quenching of Hb.     

Crystal structure and DNA binding studies of a cobalt(Ⅱ) complex containing mixed-ligands of 1,10-phenathroline and glycollic acid

A cobalt（11） complex containing mixed-ligands of 1,10-phenathroline（phen） and glycollic acid（GA）.|Co（GA）₂（phen）| was synthesized and its structure was characterized by X-ray diffraction.The interaction of the complex with DNA was investigated by electronic absorption spectra and electrochemical methods.Electronic absorption spectrum experiments showed that after interaction with DNA.the characteristic absorption peaks of |Co（GA）₂（phen）| underwent hypochromic effect as well as redshift. Also,the binding strength of 3.8×10⁴L/mol was estimated by titration method.Electrochemical assays revealed that the redox peak currents of the complex decreased obviously accompanied by a positive shift of the formal potential after association with DNA.All these results revealed that the synthesized cobalt complex bound with DNA via an intercalation mode.     

Synthesis,Crystal Structure and DNA-Binding Property of a New Cu(Ⅱ) Complex Based on 4-(Trifluoro-methyl)nicotinic Acid

A new complex[Cu_1.5(tfc)₃(H₂O)₄]·3H₂O (1,Htfc=4-(trifluoro-methyl) nicotinic acid) has been synthesized and characterized by X-ray single-crystal diffraction,elemental analysis,IR spectra and thermogravimetric analysis.1 belongs to orthorhombic system,space group Pccn with a=44.507(2),b=10.7710(6),c=11.7544(7)?,V=5634.9(6)?³,Z=1,D_c=1.803 mg·cm^-3,F(000)=3068,μ=1.266 mm^-1,the final R=0.0488and w R=0....     

Metal complex with terpyrindine derivative ligand as highly selective colorimetric sensor for iron(Ⅲ)

A new metal complex[MnL₂]（NO₃）₂·CH₃CN（1） was synthesized by reaction of 4’-4-（l,2,4-triazol-l-yl）phenyl -2,2’:6’,2"-terpyridine（L） with manganese nitrate.The structure of the complex was determined by X-ray crystallography.The results of UV-vis studies showed that the complex exhibits colorimetric sensing ability for Fe³⁺,which can be observed by naked eye.     

One novel multidimensional organic-inorganic hybrid based on polyoxometalates and copper chlorine coordination polymers with 4,4’-bipyridine ligands

One novel organic-inorganic hybrid materials with 4,4’-bipy ligands and copper chlorine coordination polymers as linkers,with new topology,{[Cu^I（4,4’-bipy）]₁₀Cl₂(SiW₁₂O₄₀)₂}·6H₂O（1）（4,4’-bipy = 4,4’-bipyridine）,has been hydrothermally synthesized. The single crystal X-ray structural analysis reveals that the structure of 1 is constructed from classical Keggin anions and[Cu^I（4,4’- bipy）]cations into a novel,three-dimensional（3D） polyoxometalates（POMs）based network.From the topological view,compound 1 is a novel（3.4⁴.5².6³）（3².4⁴.5⁶.6⁹） topology.The electrochemical and photocatalysis properties of 1 have been investigated in details.     

Tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate:Halogen-free and single-component catalysts for the coupling reaction of carbon dioxide and epichlorohydrin

The green synthesis of chloropropylene carbonate via the coupling reaction of carbon dioxide and epichlorohydrin had been achieved using halogen-free and single-component catalysts tetrabutylammonium salts of tritransition-metal-substituted A-α-tungstogermanate [（n-C₄H₉）₄N]₃H₇GeW₉M₃（H₂O）₃O₃₇（M = Cu^Ⅱ,Ni^Ⅱ,Co^Ⅱand Mn^Ⅱ） without any solvent.The catalytic activity was significantly depended on the transition metal introduced in polyoxometalates.[（n-C₄H₉）₄N]₃H₇GeW₉Mn₃（H₂O）₃O₃₇ exhibited the highest catalytic activity with 94.9%conversion for epichlorohydrin and 98%selectivity for chloropropylene carbonate in 3 h.Plausible mechanism was proposed based on the results.     

Structure and Photophysical Properties of an Upconversion Holmium-mercury Compound with a 2-D Layer-like Motif

Using a hydrothermal reaction,a novel holmium-mercury compound{[Ho(IA)(HIA)₂(H2 O)₂]_2-(Hg₃Br₈)}n(nHgBr₂)·2 nNO₃(1,HIA is isonicotinc acid)was synthesized and its crystal structure was characterized by single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic system,space group P2/c with a=13.0647(6),b=9.4659(3),c=26.0832(14)?,β=97.522(4)°,V=3197.9(2)?³,C₃₆H₃₆Br₁₀Hg₄Ho₂N₈O₂₂,M_r=2863.95,Z=2,D_c=2.974 g/cm³,μ(Mo Kα)=18.331 mm^–1 and F(000)=2575.It displays a two-dimensional(2 D)layer-like structure.A solid-state photoluminescence experiment revealed that it shows upconversion green emission.The emission peaks should come from the ⁵I₈→⁵G₆ and ⁵S₂→⁵I₈ characteristic emission of the 4 f electrons of the Ho3+ion.Compound 1 has a CIE chromaticity coordinate(0.1774,0.526).A solid-state UV-visible diffuse reflectance spectrum unveiled that this compound has a wide optical band gap of 3.26 eV.     

One Novel Ag(Ⅰ) Compound Generated from Double Schiff-base Ligand with Quinoxaline-N-oxide as Terminal Binding Sites

One novel discrete coordination molecule with Ag^I centers,namely[Ag₃(L)₃(ClO₄)₃]·3CH₂Cl₂·6CH₃OH·1.5H₂O (1),has been synthesized based on the double Schiff-base ligand,3,6-bis[2-(4-oxidequinoxaline)-yl]-4,5-diaza-3,5-octadiene (L) and AgClO_4.The obtained Ag(I) compound was fully characterized by infrared spectroscopy,elemental analysis,and single-crystal X-ray diffraction.1 is of trigonal system space group P-31c with a=16.320(2),b=16.320(2),c=20.108(6)?,T=173(2) K,V=4638.2(16) A³,D_c=1.645 g/cm³,M_r=2297.33,Z=2,F(000)=2334,μ=0.970 mm~(–1),Goodness-of-fit=1.109,the final R=0.0776,wR=0.1813,Rindices (all data)=0.1196,wR=0.2011.The compound exhibits a triple-helical[Ag₃L₃]³⁺crown-like trimer,in which three Ag(I) atoms form an equilateral triangle with the Ag···Ag distance of 4.7 A.Uncoordinated counterions ClO₄^– and solvent molecules methanol generate the hydrogen-bonded frameworks based on discrete molecular complex building blocks.     

Supramolecular assembly of Keggin polyoxomolybdate and 2,2’-bipyridine generated in situ from a decarboxylation coupling reaction

An assembly of Keggin polyoxomolybdate and organic substrate（Hbipy）₃[PMo₁₂O₄₀]（1,bipy=2,2’-bipyridine） was synthesized and characterized by elemental analysis,infrared spectrum,and single-crystal X-ray analysis.The ligand bipy of compound 1 was generated by a decarboxylation coupling reaction of H₂pdc（H₂pdc=pyridine-2,6-dicarboxylic acid） in situ under hydrothermal reaction conditions and the control experiments illustrate that La（NO₃）₃ or Ce（NO₃）₃,which does not appear in the final structure,is necessary for the decarboxylation coupling reaction.Moreover,compound 1 displays strong photoluminescence property in the solid state at room temperature.     

Methane conversion under cold plasma over Pd-containing ionic liquids immobilized on γ-Al2O3

Pd-containing ionic liquid（IL） 1-hexyl-3-methylimidazolium tetrafluoroborate（C₆MIMBF₄） immobilized on 7-Al₂O₃（Pd-IL/γ-Al₂O₃） was prepared and characterized by Fourier transform infrared spectroscopy（FTIR）,scanning electron microscopy（SEM） and Brunauer-Emmett-Teller （BET） analysis.The influences of C₆MIMBF₄ loading and Pd on methane conversion to C₂ hydrocarbons under cold plasma were investigated.FTIR and SEM analyses indicated that C₆MIMBF₄ had been successfully immobilized on 7-Al₂O₃ and the C₆MIMBF₄ showed excellent stability under cold plasma.The results of BET and methane conversion showed that with the increase in immobilization amount of C₆MIMBF₄ ontoγ-Al₂O₃,the specific surface area and pore volume of IL/γ-Al₂O₃ decreased,while the selectivity and yield of C₂ hydrocarbons increased.The selectivity of C₂ hydrocarbons was 94.6%when the loading of C₆MIMBF₄ was 40%,and the percentage of C₂H₄ in C₂ hydrocarbons was as high as 64%when using Pd-IL/γ-Al₂O₃ as a catalyst with no conventional thermal reduction treatment. Optical emission spectra（OES） from the cold plasma reactor during methane conversion were also studied.The results indicated that the intensity of the C₂,CH,H,and C active species from methane and hydrogen decomposition increased when IL/γ-Al₂O₃ or Pd-IL/γ-Al₂O₃ was introduced into the plasma system.Based on the analyses of the gas product and OES spectra,it can be concluded that the surface catalyzed reactions between plasma and ionic liquid were very important for the reduction of Pd²⁺ and the formation of C₂H₄.     

rac-11-t-Butoxy-1,4-dihydro-1,4-methanoanthracene:A two-dimensional framework structure built from C-H…O and C-H…πhydrogen bonds

The title compound rac-11-t-butoxy-l,4-dihydro-l,4-methanoanthracene(C₁₉H₂₀O,M_r = 264.35) has been synthesized and characterized by FT-IR,’H NMR,HRMS spectra and single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P2₁/n,with a = 13.5240（10）,b = 8.3453（6）,c = 13.9604（9） ,β= 100.0190（10）°.The structure of the title compound comprises a norbomene unit with a t-butoxy group,having a naphthalene ring fused on one side.The naphthalene is essentially planar with a maximum deviation of 0.032（2） for atom C（3）.In the crystal,inversion-related molecules are linked by pairs of C-H…O hydrogen bonds,forming a cyclic dimer with R₂²（16） graph-set motif.The C-H…πinteractions are also observed,linking the molecules into a continuous two-dimensional framework structure.     

Two Novel {Ti_6P_2} Clusters Decorated with Inorganic Acids

Two inorganic acids decorating titanium-oxo clusters (PTCs),Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(NO₃)₂(PTC-251) and Ti_6O_4(O~iPr)₁₀(O₃P-Phen)₂(HSO_4)₂ (PTC-252)(H₂O₃P-Phen=phenylphosphinic acid) have been synthesized under solvothermal conditions.As a result of the labile coordination sites of the{Ti_6P₂}unit,nitrite and sulfate adopt different capping mode.Besides,they also present different space packing.The photocatalytic H₂evolution activities of these obtained PTCs have been studied,with sulfate decorating PTC-252 presenting a maximum H₂ production rate up to 110.95μmol·g^-1·h^-1.     

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)₂(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H₂DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^o,V=4056.6(16)A³,Z=4,C₄₅H₂₂Cl₂F₂Mn N₁₀O₇,M_r=978.57,D_c=1.602 g/cm³,F(000)=1980,μ(Mo Ka)=0.536 mm^–1,R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^o,V=4742.0(12)A³,Z=8,C₂₇H₁₄Cl Co FN₄O₄,M_r=517.80,D_c=1.602 g/cm³,F(000)=2312,μ(Mo Ka)=0.889 mm^–1,R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.     

Synthesis,Crystal Structure,Theoretical Calculation,and Photophysical Property of a New Cd(Ⅱ) Complex Based on N-heterocyclic Ligand and Isophthalic Acid

A new metal-organic coordination complex[Cd(imp)(m-bdc)]_n (1,ipm=5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol,m-bdc=isophthalic acid) has been synthesized by hydrothermal reaction and characterized by elemental analysis,thermogravimetric (TG) analysis,infrared spectrum (IR) and single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a=15.373(5),b=16.719(5),c=19.406(6)A,β=106.995(5)°,V=4770(2)A³,C₂₈H₁₈Cd N₄O₆,M_r=618.86,D_c=1.724 g/cm³,μ(Mo Kα)=0.971 mm^–1,F(000)=2480,Z=8,the final R=0.0391 and w R=0.1044 for 4701 observed reflections (I>2σ(I)).Single-crystal X-ray diffraction reveals that 1 exhibits a one-dimensional (1D) double-chain architecture,and the H-bond intersections link the 1D double-chain architecture into a 2D layer structure.TG analysis shows clear courses of weight loss,which corresponds to the decomposition of different ligands.We also study the luminescent properties of complex 1.In addition,to elucidate the essential electronic characters of this complex,theoretical calculation analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program.     

Synthesis,Structure and Characterization of a New Silicophosphate,K_2SiP_4O_(13), with a Six-fold Coordinated Si

A potassium silicophosphate,K2SiP4O13,has been synthesized in molten polyphosphoric acid.It crystalizes in the triclinic space group P1^-(No.2)with a=4.8327(10),b=7.7403(15),c=14.485(3)?,a=82.29(3)°,β=83.31(3)°,γ=81.95°,V=529.02(19)?³,Z=2.The crystallographic structure features 2D layers of[SiP₄O₁₃]_∞in the ab plane with counter cations K⁺residing among the layers,and the anionic framework of[SiP₄O₁₃]_∞is composed of six-fold coordinated Si atoms and tetraphosphate anions by sharing vertex O atoms.The title compound was characterized by powder X-ray diffraction,IR and Raman spectroscopies,UV-vis diffuse reflectance spectroscopy,thermogravimetry and differential scanning calorimetry.     

Self-assembly of three Ag-polyoxovanadates frameworks for their efficient construction of C–N bond and detoxification of simulant sulfur mustard

Three imidazole-modified Ag-polyoxovanadates frameworks（APFs） with a controllable molar ratio of Ag+to polyoxovanadates（POVs） [Ag（IM）₂]₂V₄O₁₂·2Ag（IM）₂（APF-1）, [Ag₂（1-e IM）₄]₂[Ag（1-e IM）₂]3·2Ag（1-e IM）₂·3（1-He IM）[V₁₀O₂₈]₂（APF-2） and [Ag（1-pIM）₂]₃[HV₁₀O₂₈]·2Ag（1-pIM）₂·2H₂O（APF-3）(IM = imidaz...     

Self-assembly of three Ag-polyoxovanadates frameworks for their efficient construction of C–N bond and detoxification of simulant sulfur mustard

Three imidazole-modified Ag-polyoxovanadates frameworks（APFs） with a controllable molar ratio of Ag+to polyoxovanadates（POVs） [Ag（IM）₂]₂V₄O₁₂·2Ag（IM）₂（APF-1）, [Ag₂（1-e IM）₄]₂[Ag（1-e IM）₂]3·2Ag（1-e IM）₂·3（1-He IM）[V₁₀O₂₈]₂（APF-2） and [Ag（1-pIM）₂]₃[HV₁₀O₂₈]·2Ag（1-pIM）₂·2H₂O（APF-3）(IM = imidaz...