Syntheses and Magnetism of μ-1, 3, 5-Benzenetricarboxylato Trinuclear Manganese(Ⅱ) and Nickel(Ⅱ)Complexes

Two new manganese(Ⅱ ) trinuclear complexes and two new nickel (Ⅱ) trinuclear compIexes, namely, [Mn3 (BZT ) (Phen )6] (ClO4 )3 (complex 1 ), [Mn (BZT)· (Nphen )6] (ClO4 )3 (complex 2), [Ni3 (BZT) (Phen)6] (ClO4 )3· 5H2O (complex3) and [Ni3 (BZT ) (Nphen )6] (ClO4 )3 (complex 4 ) (BZT = 1, 3, 5-benzenetricarboxylato, Phen = 1, 10-phenthroline, Nphen = 5-nitro-1, 10-phenanthroline )have been synthesized. The complexes were characterized using elemental analysis,IR and electronic reflection spectra. These complexes are proposed to have extended 1, 3, 5-benzenetricarboxylato-bridged structure and to consist of three manganese (Ⅱ) or three nickel(Ⅱ). The X-band ESR spectra of the complex 1 and complex 2were recorded at room temperature. The variable-temperature magnetic susceptibilities of complex 1 and complex 3 were measured over 4. 2-300 K. According to experimental results of the variable-temperature magnetic susceptibility, the magnetic interaction between the paramagnetic centers is too weak to be detected using the usual magnetic susceptibility technique.

Synthesis, Crystal Structure and Theoretical Calculation of a Novel 2D Network of Manganese(Ⅱ) Complex

A novel complex, [Mn（2-NCP）（H2BTC）（H2O）]n（1, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid, 2-HNCP = 2-（2-carboxyphenyl）-1 H-imidazo（4,5-f）-（1,10）phenanthroline）, was hydrothermally synthesized and structurally characterized by elemental analysis, IR, XRD and single-crystal X-ray diffraction. Structural analyses reveal that complex 1 exhibits a（6, 6）-connected topology network with a Schl?fli symbol of（63）. The adjacent 2 D layers are further stacked via strong hydrogen-bonding interactions, giving a 3 D supramolecular framework. In addition, the structure of complex 1 was calculated by the B3LYP/LANL2 DZ method by Gaussian program. The results from natural bond orbital（NBO） analysis shows obvious covalent interaction between the coordinated atoms and Mn（Ⅱ） ion.

Synthesis and Characterization of a Homochrial Manganese(Ⅱ)Complex Constructed from (1R,2R)-(-)-Diaminocyclohexane-N,N biscarboxyl-salicylidene)

A homochrial manganese（Ⅱ） complex derived from chiral salen ligand （1R,2R）-（-）diaminocyclohexane-N,N-biscarboxyl-salicylidene） （1） has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism （CD）,powder and single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2 with a=32.987（7）,b=7.4662（15）,c=17.931（4）,β=97.82（3）°,V=4375.0（15） 3,Z=8,D c=1.544 g/cm 3,F（000）=2096,M r=508.36,μ=0.658 mm-1,the final GOOF=0.975,R=0.0676 and wR=0.2068 for 6357 observed reflections with I 2σ（Ⅰ）.The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand （MnSalen）,and the polymeric chains are further assembled into a 2D supramolecular network structure via strong intermolecular hydrogen bonding interactions between the adjacent zigzag chains.

Synthesis and Crystal Structure of a Manganese(Ⅱ) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.

Synthesis and Crystal Structure of a Three-dimensional Manganese(Ⅱ)Complex Constructed via Covalent and Hydrogen Bonds

The assembly of 1,4-benzenedicarboxylic acid (H2bdc), 4,4?bipyridine (4,4?bipy), trimethyltin chloride and MnBr24H2O in hydrothermal conditions gave rise to a hydrogen-bonded three-dimensional complex {[Mn(4,4?bipy)4H2O](bdc)}n which has been characterized by single- crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P2/n with a = 7.0001(2), b = 11.5540(3), c = 11.4192(1) ? = 101.754(2)? V = 904.21(4) 3, Z = 2, C18H20MnN2O8, Mr = 447.30, Dc = 1.643 g/cm3, F(000) = 462 and m(MoK? = 0.783 mm-1. The final R and wR are 0.0499 and 0.1301, respectively for 1335 observed reflections with I ≥ 2(I). The Mn (Ⅱ) is six-coordinated in a distorted octahedral geometry. 4,4?Bipyridine in a m-bridge mode links [Mn(H2O)4]2+ into a linear cation chain. bdc acts as a counter anion and links the linear chains into a three-dimensional structure through hydrogen bonds.

Synthesis and Crystal Structure of a Bimetallic Cyanide-bridged Complex Derived from Manganese(Ⅲ) Schiff-base Complex and Pentacyanidonitrosylferrate(Ⅱ) Building Blocks

A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.

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.

Synthesis, Crystal Structure and Spectrum Properties of Trinuclear Manganese Coordination Compound Mn_3(2,2'-bipy)_2(3,5-DMBA)_6

A novel complex Mn3（2,2＇-bipy）ff3,5-DMBA）6 with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＇-bipyridine （2,2＇-bipy） has been synthesized by means of a solvent method. It crystallizes in the monoclinic space group C2/c with a = 3.1118（6）, b = 1.1754（2）, c = 2.0887（4） nm, β = 118.50（3）°, V= 6.714（2） nm3, Dc = 1.384 g/cm3, Z = 8, F（000） = 2912, the final GOOF = 1.078, R = 0.0691 and wR = 0.1455. The crystal structure shows that the three coordinated manganese（II） ions lie in a line with the middle one as the symmetric center. The distance between the central manganese（II） and the symmetric one is 0.3549 nm. There exist two coordination modes for the three manganese （II） ions： the symmetric manganese（II） ions are coordinated with three oxygen atoms and two nitrogen atoms from three 3,5-DMBA molecules and one 2,2＇-bipy molecule, respectively, forming a distorted square-pyramidal coordination geometry; the middle manganese（II） ion is coordinated with six oxygen atoms from six 3,5-DMBA molecules, generating a distorted octahedral coordination geometry. Spectrum properties of the complex were also studied.

Hydrothermal Synthesis and Crystal Structure of a New Manganese(II) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2′-Bipyridine Ligands

A new metal-organic complex [Mn2（PDC）2（bipy）2（H2O）2] （H2PDC = 2,4-pyridine-dicarboxylic acid, bipy = 2,2′-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P ^-1 with a = 7.376（3）, b = 9.990（4）, c = 11.950（5） A^°, α= 75.217（5）, β = 78.052（5）, γ = 70.655（5）°, V = 796.0（5）A^°3, C34HE6Mn2N6O10, Mr = 788.49, De = 1.645 g/cm^3,μ（MoKa） = 0.866 mm^-1, F（000） = 235, Z = 1, the final R = 0.0425 and wR = 0.0700 for 1971 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands, one aqua ligand, and three nitrogen atoms from 2,2′-bipy and PDC ligands, giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.

Synthesis and Crystal Structure of a Three-dimensional Manganese(II) Complex (tataH)_2[Mn(pydc)_2]·4H_2O (tata = 2,4,6-Triamino-1,3,5-triazine, pydcH_2 = Pyridine-2,6-dicarboxylic Acid)

A manganese（Ⅱ） complex （tataH）2[Mn（pydc）2]·4H2O （C20H28MBN14O12, Mr = 711.50, tata = 2,4,6-triamino-1,3,5-triazine, pydcH2 = pyridine-2,6-dicarboxylic acid） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1^-, with a = 9.9847（3）, b = 10.9813（3）, c = 15.2616（5）A, a = 101.5310（10）, β = 90.2610（10）, γ = 116.4600（ 10）% V = 1459.44（8）A^3, Z = 2, Dc = 1.619 g/cm^3,μ = 0.539 mm^-1, F（000） = 734, the final R = 0.0292 and wR = 0.0745. In the crystal the Mnn atom is six-coordinated by four carbonyl oxygen atoms and two pyridine nitrogen atoms from two tridentate pydc ligands to furnish a distorted octahedral geometry. The complex shows the A…D…D＇…A＇ H-bonded tetramer. The molecules are packed in a three-dimensional framework structure by the combination of O-H…O, N-H…O and N-H…N hydrogen bonds between （tataH）^＋, [Mn（pydc）2]^2- and crystal water.

Synthesis,Crystal Structure,Spectroscopic Characterization and Thermal Stability Properties of a Trinuclear Zinc(Ⅱ) Complex

A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.

Synthesis and Crystal Structure of Mercury BridgedBiferrocene Trinuclear Complex Hg(FcL)_2,Bis(S-methyl-N-(1-ferrocenyl-1-methyl)methylenedithiocarbazate)mercury(Ⅱ)

The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.

Synthesis and Magnetism of 2-Hydroxy-1,3-propylene-bis(oxamato)-bridged Co^(Ⅱ)CuCo^(Ⅱ)CoCo^(Ⅱ)Complexes

Four new heterotrinuclear complexes have been synthesized and characterized, namely [(CoL 2) 2Cu(pbaOH)](ClO 4) 2, where pbaOH denotes 2 hydroxy 1,3 propylenebis(oxamato) and L stands for 1,10 phenanthroline(phen), 5 nitro 1,10 phenanthroline(NO 2 phen), 2,2 bipyridyl(bpy) and 4,4 dimethyl 2,2 bipyridyl(Me 2bpy). The temperature dependence of the magnetic susceptibility of [(Cophen 2) 2Cu(pbaOH)](ClO 4) 2·H 2O has been studied in the range of 4—300 K, the plot of χ M T vs. T exhibits a minimum at about 120 K, but abnormal magnetic behavior below 78 K.

若干锰(Ⅱ)配合物的合成及其清除活性氧效能的研究

合成了三种锰?配合物,通过多种物理方法进行了表征,推断了它们的结构式。用核黄素光照法测定了它们的超氧化物歧化酶活性,并对其清除多形核白细胞(PMNL)呼吸爆发产生的活性氧及黄嘌呤与黄嘌呤氧化酶体系产生的·O2-及H2O2-Fe2+产生的·OH的效能进行了研究,结果表明能降低活性氧导致的鲁米诺化学发光值;降低·O2-与DMPO加合物的ESR波谱信号,减少·O2-损伤膜提取物产生的脂类过氧化物产量;对·OH与DMPO加合物的ESR波谱无影响,说明这三种配合物确具有SOD样活性。

N,N′-双(2-吡啶甲基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及表征

０前言多原子桥联配体的多核配合物中，顺磁离子间磁偶合作用的研究对阐明磁性和结构的关系以及设计新型分子基磁性材料具有重要的理论意义。草酸根及草酰胺桥根桥联的多核配合物得到了较为广泛和深入的研究［１－５］。为了研究硫原子取代氧原子后，桥基对传递磁交换作用...

新型不对称双Schiff碱Cu(Ⅱ),Zn(Ⅱ)异三核配合物的合成和晶体结构

合成了不对称双Schiff碱Cu(Ⅱ)单核配合物CuHL(H3L为N3羧基水杨醛N′水杨醛缩乙二胺)及其Cu(Ⅱ)Zn(Ⅱ)Cu(Ⅱ)异三核配合物。用元素分析、红外光谱、电子光谱对它们进行了表征,用X射线单晶衍射法测定了三核配合物的晶体结构。该三核配合物属三斜晶系,P1空间群,晶胞参数为a=11862(2)nm,b=15440(3)nm,c=19488(4)nm;α=9004(3)°,β=9786(3)°,γ=9012(3)°;V=35356(12)nm3,Z=1;R1=00614,wR2=01319。

一种新型双核锰(Ⅱ)配合物的合成、表征及磁性能研究

以Mn(CH3COO)2·4H2O和邻羟基苯甲醛缩4-氨基安替比林为原料,采用溶剂热法成功合成出一个新型双核锰(II)配合物([Mn(L-)(CH3COO)2]HL=邻羟基苯甲醛缩4-氨基安替比林),并通过X射线单晶衍射、红外光谱、元素分析、热重分析、X-粉末衍射、磁性分析和紫外分析等手段对该配合物进行表征及性质研究。结果表明双核锰配合物属于三斜晶系,空间群为P1,晶胞参数:a=0.81298(7)nm,b=0.95766(9)nm,c=1.32046(12)nm,α=100.9290(10)°,β=90.3510(10)°,γ=108.7220(10)°,V=0.95351(15)nm3,Z=1,Dc=1.464 Mg/m3,F(000)=434,μ=0.724 mm-1,R1=0.0346,wR2=0.1106[I>2σ(I)]。

N,N′-双(2-吡啶乙基)二硫代草酰胺根桥联的异三核锰(Ⅱ)铜(Ⅱ)锰(Ⅱ)、镍(Ⅱ)铜(Ⅱ)镍(Ⅱ)和三核镍(Ⅱ)配合物的合成及性质

以取代的二硫代草酰胺根作为桥联配体,合成了3种新的三核镍配合物[Ni3(Ped)2](ClO4)2(H2O)(1)、[Ni3(Ped)2](NO3)2(H2O)(2)和[Ni3(Ped)2](Ac)2(H2O)2(3),及2种新的异三核铜镍和铜锰配合物[CuNi2(Ped)2](NO3)2(H2O)2(4)和[CuMn2(Ped)2](NO3)2(H2O)2(5)(H2Ped=N,N′-双(2-吡啶乙基)二硫代草酰胺)。通过元素分析、红外光谱、紫外可见光谱、电导、电子顺磁共振谱等对配合物进行了表征,对配合物进行了热分析。测定了配合物(5)的变温磁化率,研究了配合物(5)中Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用,结果表明在Cu(Ⅱ)-Mn(Ⅱ)离子间的磁相互作用具有高自旋基态的非正规自旋态性质。

N_2-苯浮选分光光度法测定环境水样中痕量锰(Ⅱ)(英文)

在碱性介质中,Mn(Ⅱ)离子与1-10邻二氮杂菲(phen)和四碘荧光素(TIF)在一定条件下可形成三元缔合物,该缔合物在水中不稳定,但可以在有机溶剂苯中稳定存在,据此建立了溶剂浮选和光度法联用测定痕量锰(Ⅱ)的新方法。该法具有较高的灵敏度(ε=9.6×105L.mol-1.cm-1)和良好的选择性,可用于天然水样中痕量锰(Ⅱ)的测定。