Synthesis and Characterization of a One-dimensional Chain Polymer {[Cu(4-CPOA)(3-PyOH)2(H2O)2](H2O}n

A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]·H2O}n (4-CPOA2- = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P-1with a = 7.672(2), b = 18.490(4), c = 13.271(3) (A), α = 72.81(3), β ＝ 84.64(3), γ = 87.28(3)°, V = 1026.3(4) (A)3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm-1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2- groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O-H…O hydrogen bonds.     

An Unprecedented 1D Zigzag Chain Alkaline Earth Metal Derivative {[Ba(DMF)_3(H_2O)_2][Ba(DMF)_4]_2(P_2W_(18)O_(62))}_n Containing Dawson Heteropolyanion

Most of the polyoxometalates have discrete structures of definite sizes and shapes belonging to well-known structural types, such as the Lindquist, Keggin, Dawson, Strandberg, or Anderson1–2. Linking these discrete entities to build solid-state materials…     

CRYSTAL AND MOLECULAR STRUCTURE OF [Cu_2(α-C_(10)H_7-CH_2CO_2)_4(DMF)_2](DMF)_2· H_2O

<正> The title complex crystallizes in the triclinic system, space group P1, a =11. 912(4), b = 13. 626(2), c=10. 040(3)(?), a=95. 03(2) ,β= 114. 8 (3), γ = 73. 58(3)°, V = 1418.0(?)3, Z = 1, D,= 1. 37g/cm3, F(000) = 612, R = 0. 064 for 4860 independent reflections [I>3σ(I)]. Each Cu atom is coordinated by the oxygen atoms from the C10H7CH2COO groups and DMF in a square pyramid geometry.     

EPR Study of a New Crystal of the Binuclear Copper（Ⅱ） Cluster Compound－〔Cu_2（α－C_（10）H_7CH_2CO_2）_4－（DMF）_2〕·（DMF）_2·H_2O

ＥＰＲＳｔｕｄｙｏｆａＮｅｗＣｒｙｓｔａｌｏｆｔｈｅＢｉｎｕｃｌｅａｒＣｏｐｐｅｒ（Ⅱ）ＣｌｕｓｔｅｒＣｏｍｐｏｕｎｄ－〔Ｃｕ_２（α－Ｃ_（１０）Ｈ_７ＣＨ_２ＣＯ_２）_４－（ＤＭＦ）_２〕·（ＤＭＦ）_２·Ｈ_２Ｏ￥ＳｕｎＱｉｏｎｇ－Ｌｉ；ＨｕａｎｇＸ?..     

A family of new glutarate compounds: synthesis, crystal structures of: Co(H2O)5L(1), Na2[CoL2] (2), Na2[L(H2L)4/2] (3), {[Co3(H2O)6L2](HL)2}.4H2O (4), {[Co3(H2O)6L2](HL)2}.10H2O (5), {[Co3(H2O)6L2]L2/2}.4H2O (6), and Na2{[Co3(H2O)2]L8/2].6H2O (7), and magnetic properties of 1 and 2 with H2L = HOOC-(CH2)3-COOH

Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.     

一维链状配位聚合物{[Cd2(1，8-nap)2(H2O)2](bpp)2}n的水热合成、晶体结构及荧光性质

The title complex, {[Cd₂(1,8-nap)₂(H₂O)₂](bpp)₂}_n(1), a cadmium complex based on mixed naphthalene-1,8-dicarboxylate (1,8-nap) and flexible 1,3-bi(4-pyridyl)propane (bpp) ligands, has been hydrothermally synthes-ized. It consists of a one-dimensional chain along c axis, which is derived from dimeric unit [Cd₂(1,8-nap)₂(H₂O)₂] linked by a pair of bpp ligands. In every [Cd₂(1,8-nap)₂(H₂O)₂] dimeric unit, two 1,8-nap act as bridging ligands to connect two Cd(Ⅱ) atoms, forming a sixteen-membered ring. Each Cd(Ⅱ) atom is in a distorted octahedral environment, coordinated by one aqua, two 1,8-nap and two bridging bpp ligands. In addition, two bridging bpp ligands connected two neighboring Cd(Ⅱ) atoms form a twenty-four-membered ring. The TGA and Luminescence property in solid state of complex 1 have been further studied and discussed in this paper. CCDC: 669293.     

Synthesis and Structural Characterization of a Novel 2D Supramolecular Complex {[Dy_2Zn(dinic)_4(H_2O)_8]·H_2O}n (H_2dinic = 2,5-Pyridinedicaboxylic Acid)

1INTRODUCTION Studies on the syntheses,structures,and proper-ties of lanthanide-transition metal complexes are currently of great interest not only due to their beha-viors as good models to investigate the nature of magnetic exchange interactions between3d and4f metal ions in magnetic materials but also to the fascinating coordination properties of Ln(III)[1～6].Although some infinite lanthanide(III)-transition metal compounds have been obtained by the con-ventional self-assembly reacti…     

{[Gd(DMF)3(DMSO)(H2O)3](μ-CN)[Fe(CN)5]}·2H2O的合成，结构表征和磁性

A new cyano-bridged Gadolinium^Ⅲ-Iron^Ⅲ complex {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]}·2H₂O (DMF=N,N-dimethylformamide; DMSO=dimethylsulfoxide) was synthesized by the grinding reaction method. It crysta-llizes in the triclinic, space group P1 with cell parameters: a=0.90363(2) nm, b=1.250 78(3) nm, c=1.41303(1) nm, α=93.174(1)°, β=94.406(1)°, γ=91.817(2)°, and V=1.588 87(5) nm³, D_c=1.582 g·cm^-3, Z=2, M_r=756.72, F(000)=760, μ=2.645 mm^-1. The slightly distorted square-antiprism eightfold-coordinated Gd(Ⅲ) and the approxi-mately oriented octahedrally sixfold-coordinated Fe(Ⅲ) are linked by a cyano-bridge group to construct a dinuclear compound. The {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]} species are held together via hydrogen bonds to form a three-dimensional framework. The Gd(Ⅲ)-Fe(Ⅲ) interaction is antiferromagnetic. CCDC: 223430.     

[Cu(NBOCTB)](ClO4)2·2DMF的合成、晶体结构和热分解过程研究

制备了二(N,N-二甲基甲酰胺)-高氯酸N,N,N'',N''-四[(1''-苄基-2''-苯并咪唑)甲基]-1,2-环己二胺合铜(Ⅱ){[Cu(NBOCTB)](ClO4)2·2DMF}.X射线测定表明其晶体属三斜晶系,空间群P1,晶胞参数α=1.1851(5)nm,b=1.2255(3)nm,c=2.5237(5)nm;α=92.37(2)°,β=98.01(2)°,γ=107.82(3)°,V=3.442(4)nm3,M=1403.93,Z=2,Dx=1.36g/cm3,μ=4.60cm(-1),F(000)=1470.TG-DTG技术研究结果表明,配合物的热分解过程分为以下4个阶段:(19941106-1597-1.jpg)     

Synthesis and Crystal Structure of 2D Coordination Polymer {[Cu(dps)2(DMSO)2](ClO4)2}n Based on 4,4′-Dipyridyl Sulfide

A new coordination polymer {[Cu(dps)₂(DMSO)₂](ClO₄)2}_n has been synthesized basing on 4,4′- dipyridyl sulfide. The structure of the obtained complex has been studied by single-crystal X-ray diffraction analysis.

     

Structure and magnetic properties of a dtm-bridged two-dimensional supramolecular complex {[Fe(dtm)2(H2O)2](ClO4)2 · 2H2O} n (dtm = 4,4′-ditriazolemethane)

This work presents the synthesis, crystal structure and magnetic properties of a novel dtm-bridged 2D iron(II) supramolecular complex {[Fe(dtm)₂(H₂O)₂](ClO₄)₂ · 2H₂O} _n (1). The 2D structure of (1) is formed by the incorporation of coordinative linkage and hydrogen-bonding interactions between the oxygen atoms of the anion water cluster [(ClO₄)₂ · 4H₂O]²⁻ and 1D cation complex chain {[Fe(dtm)₂(H₂O)₂]²⁻. The magnetic behavior reveals an antiferromagnetic interaction between Fe(II) ions through hydrogen bonded bridges.     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

Synthesis and Properties of [Cd(HTRTR)2(H2O)4](HTNR)2 as an Energetic Complex

The energetic complex, [Cd(HTRTR)₂(H₂O)₄](HTNR)₂ {HTRTR = 4‐[3‐(1,2,4‐triazol‐yl)‐1,2,4‐triaozle; HTNR^– = styphnic acid anion) was synthesized and characterized by FT‐IR spectroscopy, elemental analysis, and single‐crystal X‐ray diffraction. It crystallizes triclinic in space group P$\bar{1}$ [a = 8.156(2) Å, b = 8.374(2) Å, c = 13.267(4) Å, α = 84.925(11)°, β = 87.016(11)°, γ = 63.683(5)°, V = 808.9(4) ų, ρ = 1.940 g · cm^–3]. The Cd^II ion is six‐coordinate with two HTRTRs and four water molecules. The thermal stabilities were investigated by differential scanning calorimetry (DSC). Non‐isothermal reaction kinetic parameters were calculated by Kissinger's and Ozawa‐Doyle's methods to obtain E_K = 144.0 kJ · mol^–1, lgA_K = 14.22, and E_O = 144.3 kJ · mol^–1. The values of thermodynamic parameters, the peak temperature while β→0 (T_p0), free energy of activation (ΔG^≠), entropy of activation (ΔS^≠), and enthalpy of activation (ΔH^≠) were obtained. Additionally, the enthalpy of formation was calculated by Hess's law on the basis of the experimental constant‐volume heat of combustion measured by bomb calorimetry, obtaining Δ_fH°₂₉₈ = 4985.5 kJ · mol^–1. Finally, the sensitivities toward impact and friction were assessed according to relevant methods. The result indicates it as an insensitive energetic material.     

Syntheses and Crystal Structures of Ruthenium Complexes of 1,4,8,11-Tetraazacyclotetradecane, Tris(2-aminoethyl)amine (tren), and Bis(2-aminoethyl)(iminomethyl)amine. A Microporous Layered Structure Consisting of {[K(tren)](2)[RuCl(6)]}(n)()(n)()(-) and {(H(5)O(2))(4)[RuCl(6)]}(n)()(n)()(+)

The second method for the synthesis of cis-[Ru(III)Cl(2)(cyclam)]Cl (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane), with use of cis-Ru(II)Cl(2)(DMSO)(4) (DMSO = dimethyl sulfoxide) as a starting complex, is reported together with the synthesis of [Ru(II)(cyclam)(bpy)](BF(4))(2).H(2)O (2) (bpy = 2,2'-bipyridine) from 1. The syntheses of Ru complexes of tris(2-aminoethyl)amine (tren) are also reported. A reaction between K(3)[Ru(III)(ox)(3)] (ox = oxalate) and tren affords fac-[Ru(III)Cl(3)(trenH)]Cl.(1)/(2)H(2)O (3) (trenH = bis(2-aminoethyl)(2-ammonioethyl)amine = monoprotonated tren) and (H(5)O(2))(2)[K(tren)][Ru(III)Cl(6)] (4) as major products and gives fac-[Ru(III)Cl(ox)(trenH)]Cl.(3)/(2)H(2)O (5) in very low reproducibility. A reaction between 3 and bpy affords [Ru(II)(baia)(bpy)](BF(4))(2) (6) (baia = bis(2-aminoethyl)(iminomethyl)amine), in which tren undergoes a selective dehydrogenation into baia. The crystal structures of 2-6 have been determined by X-ray diffraction, and their structural features are discussed in detail. Crystallographic data are as follows: 2, RuF(8)ON(6)C(20)B(2)H(34), monoclinic, space group P2(1)/c with a = 12.448(3) ?, b = 13.200(7) ?, c = 17.973(4) ?, beta = 104.28(2) degrees, V = 2862(2) ?(3), and Z = 4; 3, RuCl(4)O(0.5)N(4)C(6)H(20), monoclinic, space group P2(1)/a with a = 13.731(2) ?, b = 14.319(4) ?, c = 13.949(2) ?, beta = 90.77(1) degrees, V = 2742(1) ?(3), and Z = 8; 4, RuKCl(6)O(4)N(4)C(6)H(28), trigonal, space group R&thremacr; with a = 10.254(4), c = 35.03(1) ?, V = 3190(2) ?(3), and Z = 6; 5, RuCl(2)O(5.5)N(4)C(8)H(22), triclinic, space group P&onemacr; with a = 10.336(2) ?, b = 14.835(2) ?, c = 10.234(1) ?, alpha = 90.28(1) degrees, beta = 90.99(1) degrees, gamma = 92.07(1) degrees, V = 1567.9(4) ?(3), and Z = 4; 6, RuF(8)N(6)C(16)B(2)H(24), monoclinic, space group P2(1)/c, a = 10.779(2) ?, b = 14.416(3) ?, c = 14.190(2) ?, beta = 93.75(2) degrees, V = 2200.3(7) ?(3), and Z = 4. Compound 4 possesses a very unique layered structure made up of both anionic and cationic slabs, {[K(tren)](2)[Ru(III)Cl(6)]}(n)()(n)()(-) and {(H(5)O(2))(4)[Ru(III)Cl(6)]}(n)()(n)()(+) (n = infinity), in which both sheets {[K(tren)](2)}(n)()(2)(n)()(+) and {(H(5)O(2))(4)}(n)()(4)(n)()(+) offer cylindrical pores that are occupied with the [Ru(III)Cl(6)](3)(-) anions. The presence of a C=N double bond of baia in 6 is judged from the C-N distance of 1.28(2) ?. It is suggested that the structural restraint enhanced by the attachment of alkylene chelates at the nitrogen donors of amines results in either the mislocation or misdirection of the donors, leading to the elongation of the Ru-N(amine) distances and to the weakening of their trans influence. Such structural strain is also discussed as related to the spectroscopic and electrochemical properties of the cis-[Ru(II)L(4)(bpy)](2+) complexes (L(4) = (NH(3))(4), (ethylenediamine)(2), and cyclam).     

新型二维异核配位聚合物{[NdBi(cydta)(NO3)2(H2O)4]&#8226;2.5H2O}n的 晶体结构与热分解

由Bi(Hcydta)&#8226;5H2O和Nd(NO3)&#8226;6H2O按1︰1的物质的量比, 在水溶液中合成了含Bi(III)-Nd(III)的异核配位聚合物{[(NO3)Nd(H2O)4(μ3-cydta)Bi(μ-ONO2)]&#8226;2.5H2O}n. 用元素分析、红外光谱、热重-差热和X射线单晶衍射等手段对标题配合物的组成和结构进行了表征. 该配合物属三斜晶系, 空间群 , 晶胞参数: a＝0.9235(3) nm, b＝1.0902(4) nm, c＝1.4253(5) nm, α＝71.840(4)°, β＝86.877(4)°, γ＝76.991(4)°, Z＝2, Mr＝936.65, V＝1.3284(8) nm3, Dc＝2.342 g&#8226; cm－3, μ＝8.646 mm－1, F(000)＝900, 最终偏离因子R1＝0.0406, wR2＝0.1124. 在该配合物中, 铋(III)与配体cydta4－的4O2N和1个硝酸根中1个O原子以及邻位分子的硝酸根形成8配位的畸变双帽三棱柱. 钕(III)与4个水分子的O, 1个硝酸根中2个O以及来自3个不同配体cydta4－的桥联羧基O结合, 形成9配位的三帽三棱柱构型. 羧酸根在Bi—Nd和硝酸根在Bi—Bi间的桥联作用, 使得整个配合物分子连接成无限二维框架结构. 热分析以及分解产物的红外光谱表明配合物热分解经历脱水、配体热分解、硝酸盐转变成氧化物等多步连续分解过程, 最后在625 ℃失重恒定.     

Three-dimensional nickel(II) and cobalt(II) coordination polymers constructed from 2,5-dichloroterephthalic acid and bis(imidazole) ligands

Two ternary mixed-ligand coordination polymers (CPs), namely [Ni(L)₂(DCTP)] _n (1) and [Co(L)(DCTP)] _n (2), have been hydrothermally synthesized by reacting different transition metal salts with 2,5-dichloroterephthalic acid (H₂DCTP) and 4,4′-[bis(imidazol-1-ylmethylene)]biphenyl (L) as ligands. Both CPs 1 and 2 were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction; CP 1 exhibits a non-interpenetrated six-connected α-Po (or pcu net) framework structure, with the point symbol {4¹²·6³}. CP 2 shows a fivefold-interpenetrating four-connected sqc6 topology with the point symbol {6⁶}. The thermal stabilities, luminescence and catalytic properties of both CPs for the degradation of methyl orange in a Fenton-like process have been investigated.     

H_(3+n)[AsMo_(12-n)V_nO_(40)]·9H_2O(n=2—4)的结构

X光晶体结构分析证实H_(3+n)[AsMo_(12-n)V_+nO_(40)]·9H_2)(n=2—4)的晶体同构,空间群为P,Z=2。n=2时,a=13.951(5),b=14.137(5),c=13.556(4),α=112.44(2),β=109.49(3),γ=60.77(3)°,V=2120.2,M_r=1943.36,D_c=3.044g.cm~(-3),μ=40.90cm~(-1),F(000)=1828。用6216个I>3σ(I)的独立衍射精修结构,R=0.082;n=3时,a=13.891(7),b=14.076(5),c=13.483(5)A,α=112.34(3),α=109.26(3),γ=60.82(3)°,V=2094.5,M_r=1899.37,D_c=3.011g.cm~(-3),μ=40.63cm~(-1),F(000)=1792。用6699个I>3σ(I)的独立衍射精修结构,R=0.054;n=4时,a=13.854(3),b=14.099(2),c=13.501(4),α=112.09(2),β=109.13(2),γ=61.03(2)°,V=2103.0,M_r=1855.38,D_c=2.92(悬浮法),D_c=2.930g.cm~(-3),μ=39.71cm~(-1),F(000)=1756。用7613个I>3σ(I)的独立衍射精修结构,R=0.044。实验采用MoKα辐射,λ=0.71073,T=296K。杂多阴离子均呈准Keggin结构,12个金属原子呈无序分布,可以M(Mo/V)表示。AsO_4四面体中As—O键长1.66—1.68,O—As—O键角均在109.5°左右。畸变的MO_6八面体中,M—O键长分布在1.63—2.36范围。水分子无序处在晶胞中十四个位置上,除O_w(12)和O_w(13)外的水分子均与杂多阴离子形成氢键,且水分子间形成如沸石中那样的复杂?     

Single-molecule magnets constructed from cyanometalates: {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Co, Ni)

Treatment of several divalent transition-metal trifluoromethanesulfonates [M(II)(OTf)2; M(II) = Mn, Co, Ni] with [NEt4][Tp*Fe(III)(CN)3] [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] in DMF affords three isostructural rectangular clusters of {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Mn, 3; Co, 4; Ni, 5) stoichiometry. Magnetic studies of 3-5 indicate that the Tp*Fe(CN)3(-) centers are highly anisotropic and exhibit antiferromagnetic (3 and 4) and ferromagnetic (5) exchange to afford S = 4, 2, and 3 spin ground states, respectively. ac susceptibility measurements suggest that 4 and 5 exhibit incipient single-molecule magnetic behavior below 2 K.     

Enantioselective resolutions and circular dichroism studies of lanthanide-containing Keggin-type [Ln(PW11O39)2](11-) polyoxometalates

Enantiopure crystals of K(1.3)Na(3.2)H(6.5)[l-Pr(PW(11)O(39))(2)]·8.3l-proline·21.5H(2)O (1), K(1.3)Na(3.2)H(6.5)[d-Pr(PW(11)O(39))(2)]·8.3d-proline·17H(2)O (2), and K(1.3)Na(3.2)H(6.5)[l-Er(PW(11)O(39))(2)]·8.3l-proline·22.5H(2)O (3) were successfully obtained by using l- and d-proline (pro) as chiral auxiliary agents. In these crystals, l- and d-[Ln(PW(11)O(39))(2)](11-) anions are attached by two l- and d-pro molecules, respectively, through a O···N hydrogen-bonding interaction between the square-antiprismatic LnO(8) center and amino-N atoms. The l- and d-[Pr(PW(11)O(39))(2)](11-) anions in aqueous solutions exhibited a couple of mirror-imaged CD spectra due to (3)H(4/2)→(3)P(0,1,2) and (1)D(2) transitions in the stereogenic Pr(3+) center. Chirality inductions by l- and d-pro from a racemic solution of [Er(PW(11)O(39))(2)](11-) was demonstrated by means of CD spectroscopy.     

Synthesis and Structural Characterization of a Ni(Ⅱ) Complex [Ni(H_2O)_4(4,4'-bipy)_2](hca)_2

1 INTRODUCTION The rational design and synthesis of new metal- organic frameworks have generated considerable interest in supramolecular chemistry and materials science owing to their intriguing structural diver- sities and potential applications as functional mate- rials[1～6]. Carboxylate-containing ligands have attrac- ted considerable attention because of the various coordination modes of carboxylate group, the ability to form hydrogen bonds and the potential applica- tions as functio…