A new ET based cation radical salt, a-(ET)2C6H4(SO3)2 (ET = bis(ethylenedithio) tetrathiafulvalene) has been synthesized by oxidative electro-crystallization and the crystal structure determined to be in monoclinic sy...A new ET based cation radical salt, a-(ET)2C6H4(SO3)2 (ET = bis(ethylenedithio) tetrathiafulvalene) has been synthesized by oxidative electro-crystallization and the crystal structure determined to be in monoclinic system, P2/n space group. Its resistivity-temperature curve shows a semi-conductive behavior with a discontinuation at about 150K.展开更多
Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all...Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.展开更多
Electro-oxidation of 3,4,3, 4-bis(ethylenedithio)-2,2,5,5-tetrathiafulvalen (abbr. ET) in the presence of allylsulfonate affords a new charge-transfer salt (ET)2(CH2=CH-CH2-SO3)H2O. The single crystal structure of the...Electro-oxidation of 3,4,3, 4-bis(ethylenedithio)-2,2,5,5-tetrathiafulvalen (abbr. ET) in the presence of allylsulfonate affords a new charge-transfer salt (ET)2(CH2=CH-CH2-SO3)H2O. The single crystal structure of the title compound is determined to be in orthorhombic crystal system, Pma2 space group. This salt is a semiconductor and its room-temperature conductivity is 0.0489Ω-1m-1.展开更多
A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The c...A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The crystallographic parameters obtained by X-ray diffraction analysis are: crthorhombic, a=10. 757(3), b=10. 763(2), c=14. 238(4)A, =1648. 9A^3; Z=2; space group Pnnm; final R=0. 047; final Rw=0. 051^(**)展开更多
A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from a system containing MoO_4^(2-),S_x^(2-),and CS_2 and characterized by IR and X-ray structural analysis. The complex crystallizes i...A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from a system containing MoO_4^(2-),S_x^(2-),and CS_2 and characterized by IR and X-ray structural analysis. The complex crystallizes in the (?)onoclinic space group P2_1/c with a=9.539(3)(?), b=20.745(2)(?),c=15.452(2)(?),β=94.58(2)°,and Z=4.The structure was solved by direct and difference Fourier synthesis methods.Least squares refinement using 2910 reflections with I>3σ(I)converged to R=0.054.The CS_3^(2-) iigand in the complex chelates to Mo atom and values of the C-S bond distances in the CS_3^(2-) ligend indicate a substantial contribution of three resonance forms.展开更多
A novel Zr-substituted polyoxometalate（POM） H2K3[Na6（H2O）9][Zr3Na3O3（H2O）3-（GeW9O（34））2]·12H2O（1） has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetr...A novel Zr-substituted polyoxometalate（POM） H2K3[Na6（H2O）9][Zr3Na3O3（H2O）3-（GeW9O（34））2]·12H2O（1） has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are： H（50）O（95）Na9K3Ge2Zr3W（1）8, hexagonal space group P63/mmc, a = 15.2251（6）, b = 15.2251（6）, c = 25.035（2） , V = 5025.7（6） 3, Z = 2, Dc = 3.716 mg/m3, μ = 21.648 mm（-1）, F（000） = 4726, the final R = 0.0259 and w R = 0.0647 for 1487 observed reflections with I 2σ（I）. Single-crystal X-ray structure analysis reveals that 1 exhibits a 3-dimensional framework structure based on Zr3Na3-substituted polyanions [Zr3Na3O3（H2O）3（GeW9O（34））2]（11-） and [Na6（H2O）9]（6＋） clusters building blocks. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the proton-conducting property of 1 was also investigated.展开更多
The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution...The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution of the component elements. The products werecharacterized by ICP, IR, UV, XRD and TG-DTA. The proton conductibility and the activation energy ofproton conduction of the heteropoly acids were investigated.展开更多
A new solid high-proton conductor,H7[Ga(H2O)P2W17O61].18H2O,a substituted heteropoly acid with Dawson structure,has been synthesized by the degradation/ion-exchange/freezing method.The product was characterized by pot...A new solid high-proton conductor,H7[Ga(H2O)P2W17O61].18H2O,a substituted heteropoly acid with Dawson structure,has been synthesized by the degradation/ion-exchange/freezing method.The product was characterized by potentiometric titration,chemical analysis,IR,UV,XRD and TG-DTA.Complex impedance measurements show a high conductivity(5.44×10-3 S/cm at 50℃),with an activation energy for proton conduction of 36.04 kJ/mol.The mechanism of proton conduction is the Vehicle mechanism.展开更多
Some new complexes RE2(EDODA)3·3H2O, where RE = La, Nd, Eu, Gd, Tb, Er, Yb, Lu and Y, EDODA = ethylene-1,2-dioxydiacetate, have been synthesized and characterized by elemental analysis, molar conductance, IR...Some new complexes RE2(EDODA)3·3H2O, where RE = La, Nd, Eu, Gd, Tb, Er, Yb, Lu and Y, EDODA = ethylene-1,2-dioxydiacetate, have been synthesized and characterized by elemental analysis, molar conductance, IR spectra, UV spectra, TG-DTA, 1H NMR and 13C NMR spectra. Various analyses indicate that the complexes are of nine-coordinated binuclear structure. The carboxylates are bidentate ligands and the ether oxygen atoms also coordinate to rare earth ions. Three water molecules are crystalline water. In addition, the influence of concentration on the chemical shift has been studied through the 1H NMR spectra of the complex Lu2(EDODA)3·3H2O in different concentrations.展开更多
A new electrical conductive crystal PyEt[Ni(dmit)2]2(dmit = 4,5-dimercapto-1,3-dithiole- 2-thione) has been synthesized and its X-ray structure has been determined to be in monoclinic system, C2/c space group. In PyEt...A new electrical conductive crystal PyEt[Ni(dmit)2]2(dmit = 4,5-dimercapto-1,3-dithiole- 2-thione) has been synthesized and its X-ray structure has been determined to be in monoclinic system, C2/c space group. In PyEt[Ni(dmit)2]2 crystal, the conducting component [Ni(dmit)2]0.5- is face-to-face packed forming molecular column along the c-direction, and these molecular columns are then side-by-side extended along the a-direction forming a kind of two-dimensional conducting sheet on(010). The measured conductivity at room temperature along a certain direction on(010) plane is 10 S·cm-1. From 282 to 269 K, the crystal shows metallic behavior but changes to semiconductor below 269 K. Based on the measured crystal structure and calculated band structure, this conductor-semiconductor phase transformation can be primarily interpreted: The metallic conductivity is corresponding to the uniform molecular column and the atomic-lattice-chain structure of Ni chain, while the semi-conductive behavior to staggered molecular column and the atomic-zigzag-chain structure of Ni chain.展开更多
A new molecular conductor (PyH)[Ni(dmit)2]2 (dmit = 4, 5-dimercapto-1, 3-dithiole-2-thione) has been prepared and its crystal structure has been determined. Crystallographic parameters for (PyH)[Ni(dmit)2]2: C17H6NNi2...A new molecular conductor (PyH)[Ni(dmit)2]2 (dmit = 4, 5-dimercapto-1, 3-dithiole-2-thione) has been prepared and its crystal structure has been determined. Crystallographic parameters for (PyH)[Ni(dmit)2]2: C17H6NNi2S20; triclinic system; P-1 space group; a = 5.9227 (4) , b =8.2279 (6), c = 16.7535 (9) A, a = 90.233 (5) , 0 = 92.107 (6) , y= 104.654 (6) ; V= 789.25 (9) A3; Z = 1; Dc = 2.068 g/cm3; F (000) = 491. The conductivity at one direction on (001) plane at room temperature was measured to be 0.13 ii^-cmf1. The resistivity-temperature curve in the temperature range of 90-290 K shows that this compound behaves as a semiconductor.展开更多
基金This project was supported by a grant for the State Key Program of China and by the National Natural Science Foundation of China (No.20172034) and also supported by the open laboratory of organic solid of Institute of Chemistry of the Chinese Academy
文摘A new ET based cation radical salt, a-(ET)2C6H4(SO3)2 (ET = bis(ethylenedithio) tetrathiafulvalene) has been synthesized by oxidative electro-crystallization and the crystal structure determined to be in monoclinic system, P2/n space group. Its resistivity-temperature curve shows a semi-conductive behavior with a discontinuation at about 150K.
基金The project was supported by Youth Science Foundation of Shandong University
文摘Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.
基金This project was supported by a grant for the State Key Program of China and by the National Natural Science Foundation of China (No.20172034) and also supported by the open laboratory of organic solid of Institute of Chemistry of the Chinese Academy o
文摘Electro-oxidation of 3,4,3, 4-bis(ethylenedithio)-2,2,5,5-tetrathiafulvalen (abbr. ET) in the presence of allylsulfonate affords a new charge-transfer salt (ET)2(CH2=CH-CH2-SO3)H2O. The single crystal structure of the title compound is determined to be in orthorhombic crystal system, Pma2 space group. This salt is a semiconductor and its room-temperature conductivity is 0.0489Ω-1m-1.
文摘A hexamolybdenum complex, [Et_4N]_2[Mo_6O_(19)H_4] crystal, with pentavalent and hexavalent molybdenum has been obtained in the solution of DMF and CH_3OH as organic solvents using MoCl_5 as a starting material. The crystallographic parameters obtained by X-ray diffraction analysis are: crthorhombic, a=10. 757(3), b=10. 763(2), c=14. 238(4)A, =1648. 9A^3; Z=2; space group Pnnm; final R=0. 047; final Rw=0. 051^(**)
文摘A new trithiocarbonato Mo complex(Et_4N)_2[(S_2)Mo2O_2(μ-S)_2(CS_3)]was obtained from a system containing MoO_4^(2-),S_x^(2-),and CS_2 and characterized by IR and X-ray structural analysis. The complex crystallizes in the (?)onoclinic space group P2_1/c with a=9.539(3)(?), b=20.745(2)(?),c=15.452(2)(?),β=94.58(2)°,and Z=4.The structure was solved by direct and difference Fourier synthesis methods.Least squares refinement using 2910 reflections with I>3σ(I)converged to R=0.054.The CS_3^(2-) iigand in the complex chelates to Mo atom and values of the C-S bond distances in the CS_3^(2-) ligend indicate a substantial contribution of three resonance forms.
基金supported by the National Natural Science Foundation of China(No.21401195)the Natural Science Foundation for young scholars of Fujian province(2015J05041)the open foundation of State Key Laboratory of Structural Chemistry(20160020)
文摘A novel Zr-substituted polyoxometalate（POM） H2K3[Na6（H2O）9][Zr3Na3O3（H2O）3-（GeW9O（34））2]·12H2O（1） has been made under hydrothermal conditions. 1 was characterized by infrared spectrum, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Crystal data are： H（50）O（95）Na9K3Ge2Zr3W（1）8, hexagonal space group P63/mmc, a = 15.2251（6）, b = 15.2251（6）, c = 25.035（2） , V = 5025.7（6） 3, Z = 2, Dc = 3.716 mg/m3, μ = 21.648 mm（-1）, F（000） = 4726, the final R = 0.0259 and w R = 0.0647 for 1487 observed reflections with I 2σ（I）. Single-crystal X-ray structure analysis reveals that 1 exhibits a 3-dimensional framework structure based on Zr3Na3-substituted polyanions [Zr3Na3O3（H2O）3（GeW9O（34））2]（11-） and [Na6（H2O）9]（6＋） clusters building blocks. UV-Vis spectrum indicates that 1 is a wide-gap semiconductor. In addition, the proton-conducting property of 1 was also investigated.
文摘The ternary germanic heteropoly acids H_5GeW_(11)O_(40) centre dot 22H_2O andH_5GeMo_(11)VO_(40) centre dot 24H_2O were synthesized for the first time by the stepwiseacidification and the stepwise addition of solution of the component elements. The products werecharacterized by ICP, IR, UV, XRD and TG-DTA. The proton conductibility and the activation energy ofproton conduction of the heteropoly acids were investigated.
基金supported by the National Natural Science Foundation of China(21071124)the Natural Science Foundation of Zhejiang Province(Y4090183)+1 种基金the Foundation of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University(2010-16)the Foundation of Key Lab of Polyoxometalates Science of the Ministry of Education of Northeast Normal University(DS-20080102)
文摘A new solid high-proton conductor,H7[Ga(H2O)P2W17O61].18H2O,a substituted heteropoly acid with Dawson structure,has been synthesized by the degradation/ion-exchange/freezing method.The product was characterized by potentiometric titration,chemical analysis,IR,UV,XRD and TG-DTA.Complex impedance measurements show a high conductivity(5.44×10-3 S/cm at 50℃),with an activation energy for proton conduction of 36.04 kJ/mol.The mechanism of proton conduction is the Vehicle mechanism.
文摘Some new complexes RE2(EDODA)3·3H2O, where RE = La, Nd, Eu, Gd, Tb, Er, Yb, Lu and Y, EDODA = ethylene-1,2-dioxydiacetate, have been synthesized and characterized by elemental analysis, molar conductance, IR spectra, UV spectra, TG-DTA, 1H NMR and 13C NMR spectra. Various analyses indicate that the complexes are of nine-coordinated binuclear structure. The carboxylates are bidentate ligands and the ether oxygen atoms also coordinate to rare earth ions. Three water molecules are crystalline water. In addition, the influence of concentration on the chemical shift has been studied through the 1H NMR spectra of the complex Lu2(EDODA)3·3H2O in different concentrations.
基金This work was supported by the National Natural Science Foundation of China(Grant No.20172034)the State Key Program of China+1 种基金the Laboratory of Organic Solidsthe ChineseAcademy of Sciences.
文摘A new electrical conductive crystal PyEt[Ni(dmit)2]2(dmit = 4,5-dimercapto-1,3-dithiole- 2-thione) has been synthesized and its X-ray structure has been determined to be in monoclinic system, C2/c space group. In PyEt[Ni(dmit)2]2 crystal, the conducting component [Ni(dmit)2]0.5- is face-to-face packed forming molecular column along the c-direction, and these molecular columns are then side-by-side extended along the a-direction forming a kind of two-dimensional conducting sheet on(010). The measured conductivity at room temperature along a certain direction on(010) plane is 10 S·cm-1. From 282 to 269 K, the crystal shows metallic behavior but changes to semiconductor below 269 K. Based on the measured crystal structure and calculated band structure, this conductor-semiconductor phase transformation can be primarily interpreted: The metallic conductivity is corresponding to the uniform molecular column and the atomic-lattice-chain structure of Ni chain, while the semi-conductive behavior to staggered molecular column and the atomic-zigzag-chain structure of Ni chain.
基金supported by the National Natural Science Foundation of China(No.20172034)the Key Laboratory of Organic Solids,the Chinese Academic of Sciences.
文摘A new molecular conductor (PyH)[Ni(dmit)2]2 (dmit = 4, 5-dimercapto-1, 3-dithiole-2-thione) has been prepared and its crystal structure has been determined. Crystallographic parameters for (PyH)[Ni(dmit)2]2: C17H6NNi2S20; triclinic system; P-1 space group; a = 5.9227 (4) , b =8.2279 (6), c = 16.7535 (9) A, a = 90.233 (5) , 0 = 92.107 (6) , y= 104.654 (6) ; V= 789.25 (9) A3; Z = 1; Dc = 2.068 g/cm3; F (000) = 491. The conductivity at one direction on (001) plane at room temperature was measured to be 0.13 ii^-cmf1. The resistivity-temperature curve in the temperature range of 90-290 K shows that this compound behaves as a semiconductor.
