A series of di-, tri- and tetranuclear lanthanide clusters with slow magnetic relaxation for Dy(2) and Dy(4)

A series of dinuclear, trinuclear and tetranuclear lanthanide complexes, formulated as [Nd(2)(Acc)(6)(H(2)O)(4)](3) [Nd(2)(Acc)(6)(H(2)O)(6)]center dot Cl(24)center dot 8H(2)O (1), [Dy(2)(Acc)(4)(H(2)O)(8)]center dot Cl(6)center dot 5.89H(2)O (2), [Ln(3)(Acc)(10)(H(2)O)(6)]center dot(ClO(4))(9)center dot 4H(2)O (Ln La, (3); Nd, (4)) and [Ln(4)(mu(3)-OH)(4)(Acc)(6)(H(2)O)(7)(ClO(4))]center dot(ClO(4))(7)center dot 11H(2)O (Ln Dy, (5); Yb, (6)), have been synthesized through the reaction of 1-amino cyclohexanel-carboxylic acid (Acc) and LnCl(3)/Ln(ClO(4))(3). Crystal structure analysis reveals that complexes 1 and 2 show dinuclear lanthanide cluster, complexes 3 and 4 have three lanthanide ions with a linear arrangement, while complexes 5 and 6 exhibit a cubane-like [Ln(4)(mu 3-OH)(4)](8+) (Ln Dy and Yb) cluster core. Their structural variations are attributed to the effect of anions and lanthanide contraction. Magnetic studies indicate that the Dy(2) and Dy(4) clusters exhibit slow relaxation of magnetization.NNSFC[20825103, 2008J0010, 90922031, 20901064]; MSTC[2007CB815304]; Natural Science Foundation of Fujian Province of China[2008J0010

pH-dependent assembly of 0D to 3D Keggin-based coordination polymers: Structures and catalytic properties

通讯作者地址: Long, LS (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R ChinaFour Keggin-based coordination polymers, namely, {[Cu-2(4,4'-bpy)(4,4'-Hbpy)(4)(H2O)(4)](-) (SiW12O40)(2)(H2O)(4)}(n) (1), {[Cu-2(4,4'-bpy)(4,4'-Hbpy)(6)(SiW12O40)(3)](4,4'-Hbpy)(2)(H2O)(7)}(n) (2), {[Cu-2(mu(2)-H2O)(2)(4,4'-bpy)(3)(SiW12O40)](H2O)(6)}(n) (3) and {[Cu-2(mu(2)-OH)(4,4'-bpy)(3)(SiW12O40)(H2O)] [Cu-2(mu(2)-O)(4,4'-bpy)(4)(H2O)(2)](0.5)center dot(H2O)(3)}(n) (4) (4,4'-bpy = 4,4'-bipyridine) were prepared through the hydrothermal reaction of silicotungstic acid, copper(II) nitrate and 4,4'-bipyridine under different pH conditions. Coordination polymers 1 and 2, which exhibit 0D and 1D structures respectively, were prepared at pH = 3.5. At pH = 5.5, a 2D coordination polymer 3 was obtained. Increasing the pH of the reaction to 8.5 led to a 3D coordination polymer 4. The structural diversities of 1-4 reveal that the pH value of the reaction plays a key role in the assembly of POM-based coordination polymers. Investigation of the catalytic properties of 1-4 for the oxidation of ethylbenzene indicates that the catalytic activity of the coordination polymers is closely related to the protonated extent of 4,4'-bpy in the coordination polymers.NNSFC 20825103 20721001 MSTC 2007CB815304 Fujian Province of China 2008J001

Construction of polyoxometalates-based coordination polymers through direct incorporation between polyoxometalates and the voids in a 2D network

通讯作者地址: Long, YX (通讯作者), Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Key Lab Analyt Sci,Minist Educ, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surface, Key Lab Analyt Sci,Minist Educ, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] series of polyoxometalates (POMs)-based coordination polymers, namely, {[Cu(2,3-Me(2)pz)(2,5-Me(2)pz)(0.5)](4)-(SiW12O40)(2,5-Me(2)pz)}(n) (2,3-Me(2)pz) =2,3-dimethylpyrazine; 2,5-Me(2)pz = 2,5-dimethylpyrazine; 1), {[Cu-2(4,4'-bipy) (4)(H2O)(4)](SiW12O40)(H2O)(18)}(n) (4,4'-bipy) 4,4'-bipyridine; 2), {[Cu(2-Mepz)(1.5)](3)(PMo12O40)(H2O)(3.5)}(n) (2-Mepz) 2-methylpyrazine; 3), {[Ag(2,3-Me(2)pz)(1.5)](4)(SiW12O40)}(n) (4), {[Cu(pz)(1.5)](4)(SiW12O40)(H2O)(3)}(n) (pz = pyrazine; 5), {[Cu(2,3-Me(2)pz)(1.5)](4)(SiW12O40)}(n) (6), {[Cu(4,4'-bipy)(1.75)](4)(SiW12O40)(H2O) 2}(n) (7), and {[Cu-2(4,4'-bipy)(4)(H2O)(4)](SiW12O40)(4,4'-bipy)(2)(H2O)(4)}(n) (8), were synthesized through direct incorporation between POMs and the voids of the 2D network. Crystal structural analysis reveals that the relationship between the size of the void of the 2D network and that of POMs is of key importance for successful synthesis of POMs-based open metal-organic frameworks. Guest replacement shows that the pore size of the framework constructed through direct incorporation between POMs and the voids of the 2D network is very sensitive to guest molecules

Beauty, Symmetry, and Magnetocaloric Effect-Four-Shell Keplerates with 104 Lanthanide Atoms

通讯作者地址: Kong, XJThe hydrolysis of Ln(ClO4)(3) in the presence of acetate leads to the assembly of the three largest known lanthanide-exclusive cluster complexes, [Nd-104(ClO4)(6)(CH3COO)(60)(mu(3)-OH)(168)(mu(4)-O)(30)(H2O)(112)].(ClO4)(18).(CH3CH2OH)(8).xH(2)O (1, x approximate to 158) and [Ln(104)(ClO4)(6)(CH3COO)(56)(mu(3)-OH)(168)(mu(4)-O)(30)(H2O)(112)].(ClO4)(22).(CH3CH2OH)(2).xH(2)O (2, Ln = Nd; 3, Ln = Gd; x approximate to 140). The structure of the common 104-lanthanide core, abbreviated as Ln(8)@Ln(48)@Ln(24)@Ln(24), features a four-shell arrangement of the metal atoms contained in an innermost cube (a Platonic solid) and, moving outward, three Archimedean solids: a truncated cuboctahedron, a truncated octahedron, and a rhombicuboctahedron. The magnetic entropy change of Delta Sm = 46.9 J kg(-1) K-1 at 2 K for Delta H = 7 T in the case of the Gd-104 cluster is the largest among previously known lanthanide-exclusive cluster compounds.973 Project from the Ministry of Science and Technology of China 2012CB821704 2014CB845601 National Natural Science Foundation of China 21422106 21371144 21431005 21390391 Foundation for the Author of National Excellent Doctoral Dissertation of China 201219 U.S. NSF APVV-0132-11 3001690 Czech Research Infrastructures LM201102

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