以α-H_(3)PMo_(12)O_(40)·nH_(2)O,La_(2)O_(3)和二甲基亚砜(DMSO)为原料,在乙腈和水的混合溶剂中制得了一维锯齿链状配位聚合物[{La(DMSO)_(6)(H_(2)O)}(PMo_(12)O_(40))·H_(2)O]_(n).X射线单晶衍射结果表明,聚合物中金属...以α-H_(3)PMo_(12)O_(40)·nH_(2)O,La_(2)O_(3)和二甲基亚砜(DMSO)为原料,在乙腈和水的混合溶剂中制得了一维锯齿链状配位聚合物[{La(DMSO)_(6)(H_(2)O)}(PMo_(12)O_(40))·H_(2)O]_(n).X射线单晶衍射结果表明,聚合物中金属配阳离子与杂多阴离子骨架通过Mo Od La Od Mo相连并形成一维无限链,每一个不对称结构单元中含一个结晶水,La^(3+)的配位数为九,三帽三棱柱构型,配位氧原子分别来自6个DMSO分子,1个H_(2)O分子和2个相邻杂多阴离子的端氧.晶体属于单斜晶系,P2_(1)/c空间群,a=13916(3)nm,b=17058(3)nm,c=24750(5)nm,β=9916(3)°,Z=4,V=5800(2)nm^(3),Dc=2825g/cm^(3),R_(1)=00446,wR_(2)=00871.IR光谱和X射线单晶衍射结果一致表明,在固态条件下配阳离子和杂多阴离子之间存在相互作用.UV光谱表明,在稀的水溶液中,由于溶剂化作用,杂多阴离子与配阳离子处于解离状态.热性质研究表明,形成标题化合物后。展开更多
利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 48...利用水热合成法合成了分子组成为(C6H11NH3)5H(P2Mo5O23)4H2O的杂多化合物, 用单晶X-ray衍射方法测定了它的结构,该晶体属于单斜晶系,空间群P21/c, a = 12.830(3), b = 14.848(3), c = 25.258(5) ? b = 92.95(3), Mr = 1483.62, V = 4805.1(17) 3, Z = 4, Dc = 2.051 g/cm3, m = 1.431 mm-1, F(000) = 3000, I >2s(I) 的可观察衍射点4426个, 最终结构偏差因子R = 0.0464, wR = 0.0801, S = 0.731。在[P2Mo5O23]6-杂多阴离子中5个MoO6八面体通过共边和共角相连, 形成1个近似的五角平面骨架, 2个PO4四面体加在五角平面的两侧。热性质研究表明杂多阴离子骨架在547.4 ℃左右分解。展开更多
A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(...A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(3), V = 1865.6(6) 3, Dc = 2.445 g/cm3, Z = 1, ?= 2.660 mm-1, Mr = 2746.56, F(000) = 1328, R = 0.0569, wR = 0.1190 and GOF = 1.125. The results of X-ray crystal analysis and IR spectrum show that there exists strong interaction between the heteropolyanions [SiMo12O40]4- and coordination cations [Mn(DMSO)5H2O]2+ in solid state.展开更多
A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra...A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra and thermal analysis studies. The result of X-ray crystallography analysis exhibits that the title compound crystallizes in the orthorhombic space group P212121, and the formula is C96H64N16Cu4SiW12O40. Crystal data： a = 18.3574（14）, b = 21.1952（16）, c = 27.992（2）A, Mr = 4570.08, V = 10891.4（14）A^3, Z = 4, Dc = 2.787 g/cm^3,μ = 13.478 mm^-1, R = 0.0364, wR = 0.0638 （I 〉 2σ（I）） and F（000） = 8360. The complex consists of one α-Keggin anion [SIW12O40]^4- and four discrete [Cu^I（phen）2]^＋ cations. The valence sum calculations for the Cu atoms suggest that all four Cu atoms are in the ＋1 oxidation state.展开更多
A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray...A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray diffraction and electrochemistry.1 crystallizes in triclinic,space group P1 with a = 12.9077（14）,b = 14.8593（16）,c = 20.023（2）,α = 70.1620（10）,β = 80.8110（10）,γ = 64.3770（10）o,V = 3256.9（6）3,Z = 2,Dc = 4.790 g/cm3,μ = 31.975 mm-1,F（000） = 4080,R = 0.0412,and wR = 0.1039.X-ray single-crystal structural analysis indicates that the molecular structural unit of 1 consists of one saturated Dawson [α-P2W18O62]6-polyanion,one seven-coordinate [Ca（H2O）2]2＋ cation,one eight-coordinate [Ca（H2O）3]2＋ cation,two protons and nine lattice water molecules.Interestingly,adjacent Dawson [α-P2W18O62]6-polyanions are connected by [Ca（H2O）2]2＋ and [Ca（H2O）3]2＋ cations and hydrogen bonding interactions to form a 3D infinite framework.The electrochemistry property of 1 has been studied.展开更多
A convenient,expeditious,and high-efficiency protocol for the transformation of alcohols into esters using a Co-modified N-doped mesoporous carbon material（Co-N/m-C）as the catalyst is proposed.The catalyst was prepa...A convenient,expeditious,and high-efficiency protocol for the transformation of alcohols into esters using a Co-modified N-doped mesoporous carbon material（Co-N/m-C）as the catalyst is proposed.The catalyst was prepared through direct pyrolysis of a macromolecular precursor.The catalyst prepared using a pyrolysis temperature of 900°C（labeled Co-N/m-C-900） exhibited the best per-formance.The strong coordination between the ultra-dispersed cobalt species and the pyridine nitrogen as well as the large area of the mesoporous surface resulted in a high turnover frequencymethyl benzoate.This value is much higher than those of state-of-the-art transition-metal-based nanocatalysts reported in the literature.Moreover,the catalyst exhibited general applicability to various structurally diverse alcohols,including benzylic,allylic,and heterocyclic alcohols,achieving the target esters in high yields.In addition,a preliminary evaluation revealed that Co-N/m-C-900 can be used six times without significant activity loss.In general,the process was rapid,simple,and cost-effective.展开更多
文摘以α-H_(3)PMo_(12)O_(40)·nH_(2)O,La_(2)O_(3)和二甲基亚砜(DMSO)为原料,在乙腈和水的混合溶剂中制得了一维锯齿链状配位聚合物[{La(DMSO)_(6)(H_(2)O)}(PMo_(12)O_(40))·H_(2)O]_(n).X射线单晶衍射结果表明,聚合物中金属配阳离子与杂多阴离子骨架通过Mo Od La Od Mo相连并形成一维无限链,每一个不对称结构单元中含一个结晶水,La^(3+)的配位数为九,三帽三棱柱构型,配位氧原子分别来自6个DMSO分子,1个H_(2)O分子和2个相邻杂多阴离子的端氧.晶体属于单斜晶系,P2_(1)/c空间群,a=13916(3)nm,b=17058(3)nm,c=24750(5)nm,β=9916(3)°,Z=4,V=5800(2)nm^(3),Dc=2825g/cm^(3),R_(1)=00446,wR_(2)=00871.IR光谱和X射线单晶衍射结果一致表明,在固态条件下配阳离子和杂多阴离子之间存在相互作用.UV光谱表明,在稀的水溶液中,由于溶剂化作用,杂多阴离子与配阳离子处于解离状态.热性质研究表明,形成标题化合物后。
基金The project was supported by the Natural Science Foundation of Henan Province (NO. 004040300) and the Outstanding Youth Foundation of Henan Province (NO. 004031800)
文摘A polyoxometalate-based complex [Mn(DMSO)5H2O]2SiMo12O40 has been synthe- sized and it crystallizes in triclinic, space group P with a = 11.863(2), b = 12.750(3), c = 13.255(3) , a = 83.62(3), b = 69.46(3), g = 87.14(3), V = 1865.6(6) 3, Dc = 2.445 g/cm3, Z = 1, ?= 2.660 mm-1, Mr = 2746.56, F(000) = 1328, R = 0.0569, wR = 0.1190 and GOF = 1.125. The results of X-ray crystal analysis and IR spectrum show that there exists strong interaction between the heteropolyanions [SiMo12O40]4- and coordination cations [Mn(DMSO)5H2O]2+ in solid state.
基金This work was supported by the Program for New Century Excellent Talents in University of Henan Province (2005HANCET-02)Natural Science Foundation of Henan Province (0611020200)
文摘A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra and thermal analysis studies. The result of X-ray crystallography analysis exhibits that the title compound crystallizes in the orthorhombic space group P212121, and the formula is C96H64N16Cu4SiW12O40. Crystal data： a = 18.3574（14）, b = 21.1952（16）, c = 27.992（2）A, Mr = 4570.08, V = 10891.4（14）A^3, Z = 4, Dc = 2.787 g/cm^3,μ = 13.478 mm^-1, R = 0.0364, wR = 0.0638 （I 〉 2σ（I）） and F（000） = 8360. The complex consists of one α-Keggin anion [SIW12O40]^4- and four discrete [Cu^I（phen）2]^＋ cations. The valence sum calculations for the Cu atoms suggest that all four Cu atoms are in the ＋1 oxidation state.
基金supported by the National Natural Science Foundation of Chinathe Program for New Century Excellent Talent in Henan University+1 种基金the Foundation of Education Department of Henan Provincethe Natural Science Foundation of Henan Province
文摘A novel 3D polyoxotungstate [Ca（H2O）2][Ca（H2O）3]H2[P2W18O62]·9H2O（1） has been synthesized by the conventional aqueous solution method and characterized by IR spectrum,elemental analyses,single-crystal X-ray diffraction and electrochemistry.1 crystallizes in triclinic,space group P1 with a = 12.9077（14）,b = 14.8593（16）,c = 20.023（2）,α = 70.1620（10）,β = 80.8110（10）,γ = 64.3770（10）o,V = 3256.9（6）3,Z = 2,Dc = 4.790 g/cm3,μ = 31.975 mm-1,F（000） = 4080,R = 0.0412,and wR = 0.1039.X-ray single-crystal structural analysis indicates that the molecular structural unit of 1 consists of one saturated Dawson [α-P2W18O62]6-polyanion,one seven-coordinate [Ca（H2O）2]2＋ cation,one eight-coordinate [Ca（H2O）3]2＋ cation,two protons and nine lattice water molecules.Interestingly,adjacent Dawson [α-P2W18O62]6-polyanions are connected by [Ca（H2O）2]2＋ and [Ca（H2O）3]2＋ cations and hydrogen bonding interactions to form a 3D infinite framework.The electrochemistry property of 1 has been studied.
基金supported by the National Natural Science Foundation of China (21773232, 21403219, 21773227)~~
文摘A convenient,expeditious,and high-efficiency protocol for the transformation of alcohols into esters using a Co-modified N-doped mesoporous carbon material（Co-N/m-C）as the catalyst is proposed.The catalyst was prepared through direct pyrolysis of a macromolecular precursor.The catalyst prepared using a pyrolysis temperature of 900°C（labeled Co-N/m-C-900） exhibited the best per-formance.The strong coordination between the ultra-dispersed cobalt species and the pyridine nitrogen as well as the large area of the mesoporous surface resulted in a high turnover frequencymethyl benzoate.This value is much higher than those of state-of-the-art transition-metal-based nanocatalysts reported in the literature.Moreover,the catalyst exhibited general applicability to various structurally diverse alcohols,including benzylic,allylic,and heterocyclic alcohols,achieving the target esters in high yields.In addition,a preliminary evaluation revealed that Co-N/m-C-900 can be used six times without significant activity loss.In general,the process was rapid,simple,and cost-effective.
