Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co（Ⅱ） coordination polymers,{[Co_3（Hchda）_2（chda）_2（bpp）_2（H_2O）_2]}_n 1 and {[Co（chda）（bpe）（H_2O）]·3H_2O}_n 2（H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis（4-pyridinyl）propane and bpe = 1,2-bis（4-pyridinyl）ethylene）,were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis（TGA）,and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square（4,4） grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.

Synthesis and Magnetic Properties of Fe（Ⅱ） and Nd（Ⅲ） Complexes of Poly（N-2-thiazolylacrylamide）

N-2-Thiazolylacrylamide （NTA） was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy （EDX） were applied to characterize these materials. The magnetic behavior of Fe（Ⅱ） and Nd（Ⅲ） complexes of poly（N-2-thiazolylacrylamide） was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd（Ⅲ） complex has an extremely high relative saturation magnetization of 35 emu/g.

Hydrothermal Synthesis, Crystal Structure and Magnetic Properties of a Novel Zero-dimensional Manganese(Ⅱ) Complex with 2,2′-Diphenic Acid and 1,10-Phenanthroline Ligands

A novel metal-organic coordination polymer [Mn3（2,2′-dipha）3（phen）6]n·3nH2O （2,2′-dipha = 2,2′-diphenic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The crystal crystallizes in triclinic, space group P1 with a = 16.921（5）, b = 18.307（5）, c = 18.450（5）A , α = 113.369（5）, β = 108.529（5）, γ = 102.984（5）°, V = 4553（2）A^ 3, C114H72Mn3N12O14.25, Mr = 2002.66, Dc = 1.461 g/cm^3, μ（MoKα） = 0.488 mm^-1, the final F（000） = 2058, Z = 2, R = 0.0491 and wR = 0.0980 for 9087 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with two carboxylate oxygen atoms from different carboxylate groups of the same dipha and four nitrogen atoms from two different phen ligands, showing a slightly distorted octahedral geometry. Fur- thermore, it exhibits a zero-dimensional structure with dipha-Mn-phen- as building units. Variable- temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.

Two Cu(II)-Nitronyl Nitroxide Complexes Including Cyclic Dimer: Synthesis, Structures and Magnetic Interactions

Using two new flexible and functional nitronyl nitroxide radicals as ligands, two copper (II) complexes {[Cu(hfac)2]3(NITmPhO3Py)2}n (1) and [Cu(hfac)2 (NIToPhO3Py)]2 (2) (NITmPhO3Py = 2-[(3-methoxy-pyridinyl)phen-3-yl]- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, NIToPhO3Py = 2-[(3-methoxy-pyridinyl)phen-2-ly]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, hfac = hexafluoroacetylacetone), have been characterized structurally and magnetically. The X-ray crystal analyses showed that complex 1 displayed a chain polymer structure which formed with {[Cu(hfac)2]3(NITmPhO3Py)2}n due to the cross-linking of two cyclic binuclear fragments {[Cu(hfac)2]2(NITmPhO3- Py)2} via the bridging unit [Cu(hfac)2];complex 2 presented a binuclear cyclic structure [Cu(hfac)2]2(NIToPhO3Py)2. The magnetic behaviors of the two complexes 1 and 2 have been investigated. Magnetic studies showed that antiferromagnetic interactions dominated in complex 1, while there existed ferromagnetic interactions between Cu(II) and coordinated NO group in complex 2.

Synthesis, crystal structures and magnetic properties of cyanide-bridged macrocyclic complexes

Three cyanide-bridged dodecanuclear macrocyclic wheel-like complexes [Cr(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (1), [Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (2) and [Co(bpmb)(CN)2]6[Mn(5-Clsalpn)]6·24H2O·8CH3CN (3) [bpmb2?= 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate dianion; 5-Brsalpn2? = N,N′-propylenebis(5-bromosalicylideneaminato) dianion; 5-Clsalpn2? = N,N′-propylenebis(5-chlorosalicylideneaminato) dianion] have been synthesized and their crystal structures and magnetic properties have been investigated. The three compounds are structurally isomorphous and consist of alternating Mn(III)-Schiff base cations and [M(bpmb)(CN)2]? anions, generating cyanide-bridged nanosized dodecanuclear macrocyclic structures with an approximate diameter of 2 nm. The study of the magnetic properties of complex 1 reveals an antiferromagnetic interaction between the Cr(III) and Mn(III) ions through the cyanide bridges. A best-fit to the magnetic susceptibility of the complex leads to a magnetic coupling constant of J CrMn = ?2.65(6) cm?1 on the basis of a one-dimensional alternating chain model with the Hamiltonian $ H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} } $ .

Chiral cyanide-bridged 1D Fe~Ⅲ-Mn~Ⅲ heterobimetallic chains: Synthesis, structures and magnetic properties

Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes: [Mn((R,R)-Salphen)Fe(Tp)(CN)3],, (1) and [Mn((S,S)-Salphen)Te(Tp)(CN)3]n (2) (Salphen = N,N'-l,2-diphenylethylenebis (salicylideneiminato) dianion, Tp = tris(pyrazolyl) hydroborate), [Mn((R,R)-Salphen)Fe(Tp*)(CN)3·2H2O],, (3) and [Mn((S,S)-Salphen)Fe(Tp*)(CN)3.2H20],, (4) (Tp* = hydridotris (3,5-dimethylpyrazol-l-yl) borate), have been successfully synthesized by the reactions of MnⅢ schiff-base complexes with the tricyanometalate building block, [(Lxp)Fe(CN)3]- (Lyp = Tp or Tp*). All complexes are made up of neutral cyano-bridged zigzag double chains with (-Fe-CN-Mn-NC-),, as the repeating unit. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Magnetic studies demonstrate that ferromagnetic interactions are operative in these complexes. The ferromagnetic couplings become weak in the chains with the bending of the Mn-N=C angles.

Two Carboxylato-bridged Binuclear Cobalt(Ⅱ) Complexes Pillared Coligands: Synthesis, Structures and Magnetic Properties

By adopting mixed-ligand strategy,two Co(Ⅱ)coordination polymers,[Co(phda)(itmb)(H2O)2]n(1)and[Co(phda)(Hpytz)]n(2)(H2phda=1,2-phenylenediacetate,itmb=1-(imidazo-1-ly)-4-(1,2,4-triazol-1-yl methyl)benzene and Hpytz=3,5-di(4-pyridyl)-1,2,4-triazolate),were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),powder X-ray diffraction(PXRD)and single-crystal X-ray diffraction.The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures.Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain,whereas complex 2 exhibits 2D open bilayers,which result from the ribbon-like carboxylate chains pillared Hpytz coligands.In addition,the magnetic susceptibilities of both compounds were measured over the temperature range of 3~300 K,and the data were analyzed well using Mag Saki software.The best fitting parameters wereκ=0.98,λ=-100 cm-1,?=588 cm-1 and J=0.6 cm-1 for complex 1 andκ=0.86,λ=-110 cm-1,?=756.8 cm-1 and J=-1.25 cm-1 for complex 2.The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.

SYNTHESIS AND MAGNETIC PROPERTY OF CARBOXYL BRIDGING DICOPPER(Ⅱ) COMPLEXES

Two new dicopper(Ⅱ) complexes with two carboxyl bridgings in one molecule[Cu(dm-phen)(HCOO)]_2(NO_3)_2 3H_2O(1). [Cu(ds-phen)(CH_3COO)]_2 (NO_3)_2 3H_2O(2). one dicopper(Ⅱ) complex with one carboxyl bridging and one hydroxo bridging in one molecule [Cu_2(OH)(C_2H_5COO)(ds-phen)_2]. (NO_3)_2 H_2O(3) and one cononuclear Cu(Ⅱ) complex [Cu(de-phen)(CF_3COO)](NO_3).H_2O(4)(dm-phen= 2,9-dimethyl-1,10-phenanthrolin)were prepared and characterized. The effective magnetic moment, u elf, was measured and their magnetic properties were discussed. The coordination modes of carboxyl moieties in all the title complexes were proposed.

Chiral cyanide-bridged 1D Fe^Ⅲ-Mn^Ⅲheterobimetallic chains:Synthesis,structures and magnetic properties

Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes: [Mn((R,R)-Salphen)Fe(Tp)(CN)3]n (1) and [Mn((S,S)-Salphen)Te(Tp)(CN)3]n (2) (Salphen = N,N'-1,2- diphenyl ethylenebis (salicylideneiminato) dianion, Tp = tris(pyrazolyl) hydroborate), [Mn((R,R)-Salphen)Fe(Tp*) (CN)3·2H2O]n (3) and [Mn((S,S)-Salphen)Fe(Tp*)(CN)3·2H2O]n (4) (Tp* = hydridotris (3Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic one-dimensional (1D) chain complexes: [Mn((R,R)-Salphen)Fe(Tp)(CN)3]n (1) and [Mn((S,S)-Salphen)Te(Tp)(CN)3]n (2) (Salphen = N,N'-1,2- diphenyl ethylenebis (salicylideneiminato) dianion, Tp = tris(pyrazolyl) hydroborate), [Mn((R,R)-Salphen)Fe(Tp*) (CN)3·2H2O]n (3) and [Mn((S,S)-Salphen)Fe(Tp*)(CN)3·2H2O]n (4) (Tp* = hydridotris (3,5-dimethylpyrazol- 1-yl) borate), have been successfully synthesized by the reactions of Mn^(Ⅲ) schiff-base complexes with the tricyanometalate building block, [(LTp)Fe(CN)3]- (LTp = Tp or Tp*). All complexes are made up of neutral cyano-bridged zigzag double chains with (-Fe-C≡N-Mn-N≡C-)n as the repeating unit. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Magnetic studies demonstrate that ferromagnetic interactions are operative in these complexes. The ferromagnetic couplings become weak in the chains with the bending of the Mn-N≡C angles.,5-dimethylpyrazol- 1-yl) borate), have been successfully synthesized by the reactions of Mn^(Ⅲ) schiff-base complexes with the tricyanometalate building block, [(LTp)Fe(CN)3]- (LTp = Tp or Tp*). All complexes are made up of neutral cyano-bridged zigzag double chains with (-Fe-C≡N-Mn-N≡C-)n as the repeating unit. Circular dichroism (CD) spectra confirm the enantiomeric nature of the optically active complexes. Magnetic studies demonstrate that ferromagnetic interactions are operative in these complexes. The ferromagnetic couplings become weak in the chains with the bending of the Mn-N≡C angles.

Hydrothermal synthesis, crystal structure and magnetic properties of a Dy~Ⅲ-Fe~Ⅲ heteronuclear complex

A new 3d-4f heteronuclear complex [Fe（phen）3]2[FeDy（H2O）（tiron）3]·6H2O （1,Na2H2tiron=disodium 4,5-dihydro-xybenzene-1,3disulfonate） was synthesized by the hydrothermal reaction. The complex crystallized in the cubic system, space group P213 with the cell parameters：a=2.18786（14）nm, V=10.4727（12）nm3 , Z=4, F（000）=4720, R1=0.0493, wR2 =0.1165, S=1.05. In each [FeDy（H2O）（tiron）3]6-unit, it was revealed that the Fe3＋ ion was in a FeO6 distorted trigonal anti-prism coordination polyhedron completed by six phenolate O atoms from three tiron 4- ligands, while Dy3＋ in a DyO7 distorted monocapped trigonal anti-prism coordination polyhedron completed by three phenolate μ2-O atoms and three O atoms from sulfonate groups of three ligands and one O atom from water. The magnetic properties of the complex was determined in the range of 2-300K, indicating the antiferromagnetic interaction between the central DyIII-FeIII ions.

Synthesis, Crystal Structure and Magnetic Property of Disodium Biscarbonato cobaltate(Ⅱ) Tetrahydrate, Na_2Co(CO_3)_2·4H_2O

The title compound, Na 2Co(CO 3) 2·4H 2O, was synthesized by dropwise addition of 1.0 mL of 1 mol/L Co(CH 3COO) 2 to 50 mL of aqueous solution containing 7.0 g(66.0 mmol) of Na 2CO 3 and 2.5 g(29.8 mmol) of NaHCO 3 under stirring. A rose colored rhombohedral crystal grew by the slow evaporation of the solution of the title compoud at room temperature. The crystal structure was established on the basis of the single crystal X ray diffraction data. Na 2Co(CO 3) 2·4H 2O crystallizes in the monoclinic space group C2/c with a =0.856 6(1) nm, b =0.714 6(1) nm, c = 1 438 7(2) nm, β =97.59(1)° , V =0.873 0(2) nm 3 , D x=2.260 g/cm 3, F (000)=596, M r=296 99, μ (Mo K α)=21.06 cm -1 , Z =4 and the final R(F) =0.032 and wR(F 2) =0.068 on the basis of 947 reflections ( F 2 ≥ 2σ(F 0 2)). The crystal consists of H 2O molecules, Na + ions and 2D 2 ∞[Co(CO 3) 2] 2- layers extending parallel to (001). H 2O molecules and Na + cations are located between the 2D layers. Each Co atom is tetrahedrally coordinated by four O atoms from four CO 2- 3 groups with d (Co\_O)=0.206 5(2) nm, 0.207 6(2) nm and the angle of O\_Co\_O is in the range of 97.7(1)°—128.5(1)°. The CO 2- 3 group bridging two Co atoms via two O atoms deviates from D 3h symmetry with d (C\_O)=0.127 2(3)\_0.129 9(3) nm and the angle of O\_C\_O is in the range of 119.5(2)°\_123.4(2)°. Each Na atom, with two close Na neighbours at 0.338 4(2) nm and 0 346 7(2) nm, respectively, is octahedrally coordinated by six O atoms from four H 2O molecules and two carbonate groups belonging to two layers with d (Na\_O)=0.232 7(2)\_0.241 1(2) nm. Of two crystallographically different H 2O molecules, one forms hydrogen bonds to two CO 3 2- groups of one 2D layer, and the other to those from two different 2D layers. Na 2Co(CO 3) 2·4H 2O is antiferromagnetic below 16 K, and between 30\_300 K its magnetic behaviour obeys Curie Weiss law χ m(cm 3·mol -1 )=2.625/( T -12.1) with μ eff =4.5 B.M. at 298 K.

SYNTHESIS, MAGNETIC PROPERTY AND X-RAY CRYSTAL STUCTURE OF MIXED VALENT COBALT COMPLEX SALT [Co~Ⅲ Cl_2(py)_4][Co~Ⅱ Cl_3(py)]

Complex salt Co_2Cl_5(py)_5 (py=pyridine) was obtained by the reaction of CoCl_2·6H_2O with Bu_4NMnO_4 in pyridine in the presence of benzoic acid. It is monoclinic and crystallizes in space group P2_1/n, fw=690.64, a=28.652(5), b=14.108(4), c=7.424(3) ;β=90.09(1); V=3001(2)~3; Z=4, Dc=1.53g/cm^3. Final R factor is 0.041. The structure consists of a discrete cation [Co~ⅢCl_2(py)_4]^+ and an anion [Co~Ⅱ Cl_3(py)]^-. The Co~Ⅲ ion is coordinated by two Cl^- and four pyridine nitrogen atoms to form an octahedral geometry, and Co~Ⅱ is coordinated by three Cl^- and one pyridine nitrogen atom to form the apices of a tetrahedron. The variable-temperature magnetic susceptility measurement shows no magnet-exchange interaction between Co~Ⅲ and Co~Ⅱ ions.

Syntheses,Crystal Structures and Magnetic Studies of Heterobimetallates Based on Paramagnetic Ruthenium(Ⅲ) Building Block [Ru~Ⅲ(salchda)(CN)2]

The syntheses, crystal structures and magnetic properties of two cyano-bridged heterobimetallic compounds prepared from a paramagnetic Ru^Ⅲ building block, transK[Ru^Ⅲ（salchda）（CN）2]（1, salchda = N,N＇-bis（salicylidene）-o-cyclohexylenediamine）, are described.1 reacts with hydrated CoCl2 and [Mn Ⅲ（salchda）（Cl）（H2O）] in MeOH to produce a trinuclear compound {[Ru^Ⅲ（salchda）（CN）]2（μ-CN）2[Co（MeOH）4]·4MeOH}n（2） and a dinuclear{[Ru^Ⅲ（salchda）（CN）]（μ-CN）[Mn^Ⅲ（salchda）（MeOH）]·2MeOH}n（3）, respectively. Both compounds exhibit intramolecular ferromagnetic coupling between Ru^Ⅲ and 3-d metal centers via the cyano bridge and intermolecular antiferromagnetic coupling. Moreover, 2 exhibits antiferromagnetic ordering below 3.4 K.

Synthesis,Crystal Structure and Luminescent/magnetic Properties of Two Metal-organic Frameworks Based on Multi-N/O-donor Mixed Ligands

Two new complexes,namely[Cd_(2)(L)(pycy)(Cl)]·2H_(2)O(1)and[Cu(HL)(H_(2)btac)]·2 H_(2)O,have been synthesized by the reaction of the corresponding metal salts with mixed ligands including 1-(1 H-imidazol-4-yl)-4-(4 H-tetrazol-5-yl)benzene(HL),2,6-pyridinedicarboxylic acid(H_(2)pycy)and 1,2,4,5-benzenetetracarboxylic acid(H4 btac),and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and powder X-ray diffraction(PXRD).Complex 1 crystallizes in triclinic,space group P1 with a=9.8938(7),b=10.1662(7),c=12.4520(8)A,α=92.7070(10),β=108.1310(10),γ=105.3230(10)°,V=1136.44(13)A^(3),Z=2,C_(17)H_(12)N_(7)O_(6)Cl Cd_(2),M_(r)=670.59,D_(c)=1.960 g/cm^(3),μ=2.037 mm^(-1),S=1.062,F(000)=648,the final R=0.0532 and w R=0.1651 for 12156 observed reflections(I>2σ(I)).Complex 2 crystallizes in triclinic,space group P1 with a=7.3058(8),b=7.4890(8),c=10.8937(12)?,α=71.3810(10),β=84.134(2),γ=65.745(2)°,V=514.68(10)A^(3),Z=1,C_(20)H_(16)Cu N_(6)O_(10),M_(r)=563.94,D_(c)=1.819 g/cm^(3),μ=1.139 mm^(-1),S=1.187,F(000)=287,the final R=0.0314 and w R=0.0807 for 3564 observed reflections(I>2σ(I)).Single-crystal X-ray structural analysis reveals that complex 1 features a trinodal(3,3,4)-connected two-dimensional(2 D)net layer with Schlafli symbol(4·6·8)(4·6^(2)·8^(3))(6^(2)·8)while 2 has a 2 D network with 4^(4)sql topology.Moreover,the photoluminescent property of 1 and magnetic property of 2 were also discussed.

三维蜂窝状配位聚合物{[Ni(tn)][Ni(CN)_4]·2H_2O}_n的合成、晶体结构及磁性质

将Ni(tn) (ClO4) 2 的水溶液和K2 [Ni(CN) 4 ]·H2 O的水溶液在U形管中通过扩散反应 ,得到了一种结构新颖的三维蜂窝状配位聚合物 {[Ni(tn) ] [Ni(CN) 4 ]·2H2 O}n(tn为 1,3 丙二胺 ) .该化合物属单斜晶系 ,空间群为C2 /c ,晶胞参数为a =1 2 0 14 ( 2 )nm ,b =0 8942 ( 2 )nm ,c =1 2 64 5 ( 3 )nm ,α =90° ,β =10 8 76( 2 )° ,γ =90° ,V =1 2 863 ( 5 )nm3 和Z =4.该化合物由四配位Ni与六配位Ni通过氰根离子桥联而形成三维无限伸展的蜂窝状结构 ,其中四配位的Ni( 2 )离子为C配位平面四方构型 ,六配位的Ni( 1)离子为N配位八面体构型 .变温磁化率测定表明 。

新型氰基桥联配位聚合物[Ni(en)_(2)]_(2)[Ni(CN)_(4)]_(2)·5H_(2)O的合成、晶体结构和磁性质

A new cyano bridged assembly,2·5H2O, prepared by slow diffusion of an aqueous solution of K2 and an aqueous solution of ClO4 in an U tube, has been characterized by X ray structure analysis, IR and magnetic measurements. The crystal crystallizes in orthorhombic, space group Pnna, a=2.8189(5)nm, b=0.8407(2)nm, c=1.4554(2)nm, V= 3.4491(11)nm3 and Z=4. The complex is built up of infinite chains which are formed by trans Ni(en)2 μ (NC)2, cis μ (NC)2Ni(CN)2 and cis μ (CN)2Ni(en)2 groups. The variable temperature magnetic susceptibility has been measured in the 5～300K range. A magnetic susceptibility study indicates the presence of a weak antiferromagnetic interaction and gives it’s weiss constant θ=2.6K. CCDC: 207329.

单分子磁体[Mn_4(CF_3COO)_4(hmp)_6]的合成、晶体结构及磁学性质

以[Mn12O12(CF3COO)16(H2O)4]·2CF3COOH·4H2O和2-羟甲基吡啶(hmpH)为起始物,在四氢呋喃溶液中合成了一种新的四核锰配合物[Mn4(CF3COO)4(hmp)6].X射线单晶衍射结果表明,该配合物属于单斜晶系,P21/c空间群,晶胞参数a=1.3663(3)nm,b=1.4705(3)nm,c=1.4734(3)nm,β=98.51(3)°,V=2.9276nm3,Z=2.配合物中有两个CF3COO-基团与七配位Mn2中心相连,其中一个为单齿配体,另一个是双齿配体.直流磁化率研究结果表明,该配合物具有较高的自旋基态,而交流磁化率依赖于外场频率变化极值的出现表明该配合物是一种单分子磁体.

[Ho_2(phen)_4(H_2O)_4(OH)_2](phen)_2(NO_3)_4的合成、晶体结构及磁性

在甲醇与水的混合溶剂中 ,经浓硝酸硝化的Ho2 O3 与 1,10 邻菲啉反应形成氢氧根桥联的双核钬配合物[Ho2 (phen) 4(H2 O) 4(OH) 2 ](phen) 2 (NO3 ) 4(phen =1,10 邻菲啉 ) .单晶X射线衍射晶体结构测定表明晶体属三斜晶系 ,P 1(no .2 )空间群 ,晶胞参数a =1.12 41(1)nm ,b =1.1439(1)nm ,c =1.40 5 8(1)nm ,α =93.989(7)°,β =98.173(7)° ,γ =10 8.19(1)°,V =1.6 874(4 )nm3 ,Z =1,Dc=1.737g/cm3 ,F(0 0 0 ) =880 ,775 2个独立衍射点中 ,5 70 2个可观测点满足Fo2 ≥ 2σ(Fo2 ) ,R1=0 .0 499,wR2 =0 .0 85 8.标题配合物由中心对称的双核 [Ho2 (phen) 4(H2 O) 4 (OH) 2 ]4 + 配阳离子 ,邻菲啉phen分子及硝酸根NO-3 阴离子组成 .每个稀土原子与 2个邻菲啉配体 ,2个水分子和 2个氢氧根配位形成配位数为 8的 [HoN4 O4 ]四方反棱柱 .配位多面体通过两氢氧根基团形成共棱的 [Ho2 N8O6]双四方反棱柱 [d(Ho—N) =0 .2 5 49～ 0 .2 5 6 5nm ,d(Ho—OH2 O) =0 .2 35 6 ,0 .2 36 6nm ,d(Ho—OOH) =0 .2 2 2 3,0 .2 2 40nm].通过氢键和芳环堆积作用 ,配阳离子和邻菲啉分子排列形成平行于 (10 1)的两维层结构 ,NO-3 阴离子位于层之间 .标题配合物为顺磁物质 ,在 5～ 30 0K区间内遵循Curie Weiss定律 ?

含双噻唑高分子及其螯合物的制备和磁性能研究进展

设计和合成有机及高分子磁性材料是当前国内外十分关注的课题,本课题组在先前研究的基础上,以电子理论和磁性理论为指导,从分子设计出发,合成出含双噻唑新型芳杂环聚合物及其过渡金属离子或稀土离子螯合物,测定了它们的磁性能,研究高分子结构、螯合物组成与磁性能的关系,探索产生磁性的机理.发现本研究体系的高分子螯合物具有顺磁居里温度(Tp)高,剩余磁场(Mr)少,矫顽力(Hc)低,是一类很好的软磁性材料,呈现出有一定特色的磁性能.本文综述了含双噻唑高分子过渡金属螯合物、稀土金属螯合物、纳米碳管接枝高分子及其螯合物的制备和磁性能研究,以及典型螯合物的非常规磁性现象的发现和机理探索研究.

对苯二甲酸根桥联的双核铬(Ⅲ)配合物的合成与磁性

以对苯二甲酸根 ( TPHA)为桥联配体 ,分别端接 4 ,4 -二甲基 -2 ,2 -联吡啶 ( Me2 bpy) ,2 ,9-二甲基 -1 ,1 0 -邻菲 啉 ( Me2 phen)和 5-氯 -1 ,1 0 -邻菲 啉 ( Cl-phen) ,合成了 3种新的双核铬 ( )配合物 [Cr2 -( TPHA) ( Me2 bpy) 4]( NO3) 4( 1 ) ,[Cr2 ( TPHA) ( Me2 phen) 4]( NO3) 4( 2 )和 [Cr2 ( TPHA) ( Clphen) 4]( NO3) 4( 3) .经元素分析、摩尔电导和磁性测定以及红外光谱和电子光谱等手段 ,推定这些配合物具有 TPHA桥联双核铬( )结构 ,其中 ,每个铬 ( )离子处于畸变八面体配位环境 .测定了配合物 ( 1 )的变温磁化率 ( 4～ 30 0 K) ,其数值用最小二乘法和从自旋 Hamiltonian算符 ( H=-2 JS1 S2 )导出的磁方程拟合 ,求得交换积分为-2 .98cm- 1 ,结果表明双核配合物中金属离子间存在弱的反铁磁自旋交换作用 .