A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence ...A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.展开更多
The title complex,[Ag 2 （L1） 2 （Pyr）·2.5H 2 O] 1 （L1=6-amino-1-naphthalenesulfonate anion,Pyr=pyrazine）,has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in...The title complex,[Ag 2 （L1） 2 （Pyr）·2.5H 2 O] 1 （L1=6-amino-1-naphthalenesulfonate anion,Pyr=pyrazine）,has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in triclinic,space group P1,with a=7.339（5）,b=13.105（5）,c=14.097（5）,α=84.377（5）,β=76.921（5）,γ=79.628（5）°,V=1296.7（11） 3,C 48 H 50 Ag 4 N 8 O 17 S 4,M r=1570.68,Z=1,D c=2.011 g/cm 3,μ=1.732 mm-1,F（000）=782,S=1.148,the final R=0.0436 and wR=0.1181 for 4130 observer reflections （I 2σ（Ⅰ））.Compound 1 shows a rare one-dimensional （1D） double chain,and the chains are further connected through secondary bonding,hydrogen bonds,and π-π interactions to generate a three-dimensional （3D） supramolecular structure.The luminescent property of 1 was also studied in the solid state at room temperture.展开更多
The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio cal...The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.展开更多
Two binuclear silver complexes, [Ag2{μ-S2P（OCH2Ph）2}2（phen）2] （1） and [Ag2{μ- SEP（OCH2CH2Ph）2}E（phen）2] （2）, were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetri...Two binuclear silver complexes, [Ag2{μ-S2P（OCH2Ph）2}2（phen）2] （1） and [Ag2{μ- SEP（OCH2CH2Ph）2}E（phen）2] （2）, were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetric analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in the triclinic system, space group P1 with a = 9.7881（4）, b = 10.7726（4）, c = 13.1952（6） A, a = 103.686（4）, ,8= 99.477（3）, ）, = 107.494（4）°, F= 1246.88（9）A3, Dc = 1.591 g.m-3 and Z = 1; Complex 2 is of monoclinic system, space group P2jn with a = 10.6014（8）, b = 24.3969（15）, c = 11.5353（10）A,β= 14.125（10）°, F= 2722.9（4） A3, Dc = 1.526 g.m-3 and Z = 2. In the molecules of 1 and 2, O,O＇-dialkyldithiophosphate anions, （PhCHEO）PS2 and （PhCH2CHEO）PS2 act as bridging ligands and connect two Ag（I） centers into a binuclear unit with AgES4P2 eight-membered rings in ＂chair＂ conformations. In both crystal structures, face-to-face π-π stacking interactions between the adjacent paralleling aromatic rings of 1,10-phenanthroline play a prominent role in the crystal packing and result in a 1D chain. And such 1D chains are further linked into 3D networks by weak intermolecular C-H...π interactions for 1.展开更多
The cyclic voltammetry(CV) and the square wave technique were used for the investigations of thallium(Ⅰ) underpotential deposition(UPD) on the silver electrode. A solution of 10 \{mmol/L\} HClO 4+10 mmol/L NaCl was s...The cyclic voltammetry(CV) and the square wave technique were used for the investigations of thallium(Ⅰ) underpotential deposition(UPD) on the silver electrode. A solution of 10 \{mmol/L\} HClO 4+10 mmol/L NaCl was selected as the supporting electrolyte. The calibration plots for Tl(Ⅰ) concentration in the range of 2×10 -9 -1×10 -7 mol/L were obtained. The detection limit was 5×10 -10 mol/L. For the solutions of 4 0×10 -9 mol/L thallium added before the urine sample pretreatment procedure, the average recovery was 105 6% with a relative standard deviation(RSD) of 15 5%.展开更多
The reaction of 2-nitro-（2-pyridylsulfanylmethyl）benzene L with silver nitrate produces a centrosymmetric binuclear complex bis（2-nitro-（2-pyridylsulfanylmethyl）benzene-N,S）- bis（nitrato-O,O）-disilver（Ⅰ）, [...The reaction of 2-nitro-（2-pyridylsulfanylmethyl）benzene L with silver nitrate produces a centrosymmetric binuclear complex bis（2-nitro-（2-pyridylsulfanylmethyl）benzene-N,S）- bis（nitrato-O,O）-disilver（Ⅰ）, [AgLNO3]2 1. The crystal is of triclinic, space group PI, with a = 7.383 （3）, b = 8.340（3）, c = 12..003（4） A, a = 95.069（6）, β = 93.498（5）, γ = 102.734（6）°, C24H20Ag2N6- O10S2, Mr= 832.32, V = 715.6（4） ,A^3, Z = 1, Dc = 1.931 g/cm^3, F（000） = 412,μ = 1.581 mm^-1, R= 0.0351 and wR = 0.0749 Each silver atom is tetrahedrally coordinated by two O atoms from bidentate nitrate, one S atom from a ligand and one N atom from another ligand. Furthermore, Ag- Ag interactions have been observed in the complex.展开更多
Two novel coordination compounds, [Zn（CBPP）2（H2O）2]·3H2O（1） and[Ag（CBPP）·2H2O]（2）（HCBPP = 1-（4？-carboxylatobenzyl）-3-（pyrazin-2-yl）pyrazole）, were hydrothermally synthesized and characterize...Two novel coordination compounds, [Zn（CBPP）2（H2O）2]·3H2O（1） and[Ag（CBPP）·2H2O]（2）（HCBPP = 1-（4？-carboxylatobenzyl）-3-（pyrazin-2-yl）pyrazole）, were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221（4）, b = 8.4211（7）, c = 14.295（3）A, β = 114.561（8）°, V = 2705.9（2） A3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F（000） = 1416, μ（Mo Kα） = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections（I 〉 2σ（I））, and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn（II） atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn（II） ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544（1）, b = 11.7195（3）, c = 19.3188（4）A, β = 94.297（2）°, V = 1434.64（5） A3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F（000） = 816, μ（Mo Kα） = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections（I 〉 2σ（I））, and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag（I） atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.展开更多
Silver（Ⅰ） oxide was applied to the selective p-tosylation of hydroxyls of saccharide. The reaction of p-methylphenyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside（A） with a stoichiometric amount of p-toluenesulfo...Silver（Ⅰ） oxide was applied to the selective p-tosylation of hydroxyls of saccharide. The reaction of p-methylphenyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside（A） with a stoichiometric amount of p-toluenesulfonyl chloride（TsCl） in the presence of silver（Ⅰ） oxide and a catalytic amount of potassium iodide selectively led to the monotosylate derivative:p-methylphenyl 3-O-p-toluenesulfonyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside（B） in a high yield（97%）. A possible mechanism of the reaction is proposed. The rational reaction process is that at n（TsCl）∶n（Ag2O）∶n（A）∶n（KI）=1.2∶1.5∶1.0∶0.2, the mixture is stirred at room temperature for 8 h, 2.74 g（97%）B could be isolated from 2.0 g of compound A.展开更多
基金supported by the Postdoctoral Science Foundation of Central South University
文摘A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.
基金supported by the Science Foundation of Suihua University (K1001005)
文摘The title complex,[Ag 2 （L1） 2 （Pyr）·2.5H 2 O] 1 （L1=6-amino-1-naphthalenesulfonate anion,Pyr=pyrazine）,has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in triclinic,space group P1,with a=7.339（5）,b=13.105（5）,c=14.097（5）,α=84.377（5）,β=76.921（5）,γ=79.628（5）°,V=1296.7（11） 3,C 48 H 50 Ag 4 N 8 O 17 S 4,M r=1570.68,Z=1,D c=2.011 g/cm 3,μ=1.732 mm-1,F（000）=782,S=1.148,the final R=0.0436 and wR=0.1181 for 4130 observer reflections （I 2σ（Ⅰ））.Compound 1 shows a rare one-dimensional （1D） double chain,and the chains are further connected through secondary bonding,hydrogen bonds,and π-π interactions to generate a three-dimensional （3D） supramolecular structure.The luminescent property of 1 was also studied in the solid state at room temperture.
文摘The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.
基金supported by the project of Science&Technology Department of Sichuan Province(2011JY0052,2012JY0115)Sichuan University of Science&Engineering(2012PY04,2012PY14,2012KY12)University Key Laboratory of Green Chemistry of Sichuan Institutes of Higher Education(LZJ1203,LYJ1301,LYJ1306)
文摘Two binuclear silver complexes, [Ag2{μ-S2P（OCH2Ph）2}2（phen）2] （1） and [Ag2{μ- SEP（OCH2CH2Ph）2}E（phen）2] （2）, were synthesized and characterized by elemental analysis, infrared spectrum, thermo-gravimetric analysis and X-ray single-crystal diffraction. Complex 1 crystallizes in the triclinic system, space group P1 with a = 9.7881（4）, b = 10.7726（4）, c = 13.1952（6） A, a = 103.686（4）, ,8= 99.477（3）, ）, = 107.494（4）°, F= 1246.88（9）A3, Dc = 1.591 g.m-3 and Z = 1; Complex 2 is of monoclinic system, space group P2jn with a = 10.6014（8）, b = 24.3969（15）, c = 11.5353（10）A,β= 14.125（10）°, F= 2722.9（4） A3, Dc = 1.526 g.m-3 and Z = 2. In the molecules of 1 and 2, O,O＇-dialkyldithiophosphate anions, （PhCHEO）PS2 and （PhCH2CHEO）PS2 act as bridging ligands and connect two Ag（I） centers into a binuclear unit with AgES4P2 eight-membered rings in ＂chair＂ conformations. In both crystal structures, face-to-face π-π stacking interactions between the adjacent paralleling aromatic rings of 1,10-phenanthroline play a prominent role in the crystal packing and result in a 1D chain. And such 1D chains are further linked into 3D networks by weak intermolecular C-H...π interactions for 1.
文摘The cyclic voltammetry(CV) and the square wave technique were used for the investigations of thallium(Ⅰ) underpotential deposition(UPD) on the silver electrode. A solution of 10 \{mmol/L\} HClO 4+10 mmol/L NaCl was selected as the supporting electrolyte. The calibration plots for Tl(Ⅰ) concentration in the range of 2×10 -9 -1×10 -7 mol/L were obtained. The detection limit was 5×10 -10 mol/L. For the solutions of 4 0×10 -9 mol/L thallium added before the urine sample pretreatment procedure, the average recovery was 105 6% with a relative standard deviation(RSD) of 15 5%.
基金The Science Foundation of University of Science and Technology of Suzhou
文摘The reaction of 2-nitro-（2-pyridylsulfanylmethyl）benzene L with silver nitrate produces a centrosymmetric binuclear complex bis（2-nitro-（2-pyridylsulfanylmethyl）benzene-N,S）- bis（nitrato-O,O）-disilver（Ⅰ）, [AgLNO3]2 1. The crystal is of triclinic, space group PI, with a = 7.383 （3）, b = 8.340（3）, c = 12..003（4） A, a = 95.069（6）, β = 93.498（5）, γ = 102.734（6）°, C24H20Ag2N6- O10S2, Mr= 832.32, V = 715.6（4） ,A^3, Z = 1, Dc = 1.931 g/cm^3, F（000） = 412,μ = 1.581 mm^-1, R= 0.0351 and wR = 0.0749 Each silver atom is tetrahedrally coordinated by two O atoms from bidentate nitrate, one S atom from a ligand and one N atom from another ligand. Furthermore, Ag- Ag interactions have been observed in the complex.
基金financially supported by the National Natural Science Foundation of China(21571034)the Natural Science Foundation of Fujian Province(2014J01033)
文摘Two novel coordination compounds, [Zn（CBPP）2（H2O）2]·3H2O（1） and[Ag（CBPP）·2H2O]（2）（HCBPP = 1-（4？-carboxylatobenzyl）-3-（pyrazin-2-yl）pyrazole）, were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221（4）, b = 8.4211（7）, c = 14.295（3）A, β = 114.561（8）°, V = 2705.9（2） A3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F（000） = 1416, μ（Mo Kα） = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections（I 〉 2σ（I））, and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn（II） atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn（II） ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544（1）, b = 11.7195（3）, c = 19.3188（4）A, β = 94.297（2）°, V = 1434.64（5） A3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F（000） = 816, μ（Mo Kα） = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections（I 〉 2σ（I））, and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag（I） atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.
文摘Silver（Ⅰ） oxide was applied to the selective p-tosylation of hydroxyls of saccharide. The reaction of p-methylphenyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside（A） with a stoichiometric amount of p-toluenesulfonyl chloride（TsCl） in the presence of silver（Ⅰ） oxide and a catalytic amount of potassium iodide selectively led to the monotosylate derivative:p-methylphenyl 3-O-p-toluenesulfonyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside（B） in a high yield（97%）. A possible mechanism of the reaction is proposed. The rational reaction process is that at n（TsCl）∶n（Ag2O）∶n（A）∶n（KI）=1.2∶1.5∶1.0∶0.2, the mixture is stirred at room temperature for 8 h, 2.74 g（97%）B could be isolated from 2.0 g of compound A.
