Rh（100）c（2×2）Mn表面合金的氧化和吸附CO的研究

用高分辨电子能量损失谱 ( HREEL S) ,研究了 Rh( 10 0 ) c( 2× 2 ) Mn表面合金的氧化及 CO在清洁和氧化表面合金上的吸附 .结果表明 ,在 Rh( 10 0 ) c( 2× 2 ) Mn氧化过程中 ,发生 Mn的偏析 ,Mn被氧化生成 Mn O薄层 .Mn- O- Rh间的强相互作用 ,使部分锰氧化物在 12 0 0 K下存在于 Rh( 10 0 )表面 .若这种表面在 70 0～ 80 0 K继续被氧化 ,可得到 Mn O1 + x/ Rh( 10 0 ) ;Mn O1 + x/ Rh( 10 0 )在 5 0 0～ 60 0 K还原后生成 Mn O/ Rh( 10 0 ) . CO吸附于Rh ( 10 0 ) c( 2× 2 ) Mn中 Rh原子的顶位 ,C- O键级比清洁 Rh( 10 0 )顶位吸附的 CO键级略低 . Mn O/ Rh( 10 0 )和Mn O1 + x/ Rh( 10 0 )上 CO吸附于经还原的、未被锰氧化物覆盖的 Rh( 10 0 )区域 ,CO与锰氧化物间可发生相互作用 .     

[Mn(phen)3](ClO4)2(H2O)·0.5(azpy)的合成和晶体结构

锰在生物体系的新陈代谢过程中有重要作用。锰有机配合物的研究成为生物无机化学研究领域的一个热点[1]。本文报道用高氯酸锰、1,10 邻菲咯啉和4,4 偶氮联吡啶[2 4]合成的锰配合物[Mn(phen)3](ClO4)2(H2O)·0 5(azpy)的晶体结构。1　实验部分1 1　Mn(Ⅱ)配合物的合成将0 0724g(0 2mmol)Mn(ClO4)2·6H2O溶于8mL水,缓慢加入含有0 1190g(0 6mmol)1,10 邻菲咯啉(phen)和0 0277g(0 15mmol)4,4′ 偶氮联吡啶(azpy)的15mL甲醇溶液,搅拌0 5h,室温下静置,一周后得[Mn(phen)3](ClO4)2(H2O)·0 5(azpy)晶体。元素分析(计算值)/%:C54 19(54 …     

一种锰的超分子化合物的制备、结构及非线性光学 性质研究

用MnSO4·H2O,KSCN,六次甲基四胺(HMTA)制备出超分子化合物[Mn(NCS)2(H2O)2(HMTA)2][Mn(NCS)2(H2O)4](H2O)2,并测定了其晶体结构。该化合物由[Mn(NCS)2(H2O)2(HMTA)2],[Mn(NCS)2(H2O)4]和H2O三部分组成,每一个HMTA配体中仅有一个N原子与Mn原子配位,剩余的3个N分别与[Mn(NCS)2(H2O)4]中的H2O及结晶H2O之间形成氢键。[Mn(NCS)2(H2O)2(HMTA)2]和[Mn(NCS)2(H2O)4]之间通过N…H—O氢键边接成无限延伸的线性长链,链与链、以及链和结晶H2O之间通过七种形式的氢键构成三维结构的超分子。用Z-扫描法测定该化合物在DMF溶液中的三阶非线性光学性质,发现它具有自聚焦效应,三阶非线性折射系数n2=9.52×10^-9m^2·W^-1,非线性极化率χ^(3)=3.41×10^-12esu.     

Synthesis,Crystal Structure and Characterization of a New Coordination Polymer Based on Trinuclear Mn（Ⅱ） Cluster：[Mn3（L）2（adip）3]·2H2O

The coordination polymer,[Mn3(L) 2(adip) 3]·2H2O(L = 2-(4-fluorophenyl) -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid) ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1 with a = 8.4085(11) ,b = 11.1273(14) ,c = 14.5758(18) ,α = 78.528(2) ,β = 75.425(2) ,γ = 78.143(2) °,V = 1276.0(3) 3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm3,F(000) = 647,μ(MoKa) = 0.819 mm-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn(Ⅱ) clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.     

Synthesis and Crystal Structure of a Cu2+ Supra-molecular Complex [Na2Cu(BTA)2(H2O)8]·H2Owith a Three-dimensional Network Structure

A three-dimensional Cu2+ supramolecular complex [Na2Cu(BTA)2(H2O)8]·H2O 1 (H2BTA = bistetrazolylamine) was synthesized by reacting the aqueous solution of CuSO4·5H2O and H2BTA under stirring. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The result indicates that 1 crystallizes in triclinic,space group P1,with a = 7.0518(2),b = 12.2692(2),c = 13.8583(3) ,α = 115.7260(10),β = 93.2440(10),γ = 98.3610(10)o,Mr = 573.90,V = 1059.01(4) 3,Z = 2,Dc = 1.800 g·cm-3,μ(MoKα) = 1.155 mm-1,F(000) = 586.0,S = 1.074,the final R = 0.0273 and wR = 0.0744 for 4334 observed reflections with Ⅰ > 2σ(Ⅰ). The Cu2+ ion is five-coordinated with a N4O1 donor set with τ = 0.153 according to the method of Addison et al. And the Na+ ions form an infinite main chain through bridging O atoms from coordinated water molecules. In 1,a three-dimensional supramolecular network is formed by O-H···O,O-H···N,N-H···O and N-H···N hydrogen bonds.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn(H2BPTC)(tpy)(H2O)]·(H2O)3}n (1, H4BPTC = 1,1′- biphenyl-2,2′,6,6′-tetracarboxylic acid, tby = 2,2′:6,2′′-terpyridine) has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971(2), b = 20.776(4), c = 14.332(3) , β = 109.25(3)o, MnC31H27N3O12, Mr = 688.50, V = 3084.1(10) 3, Dc = 1.483 g/cm3, F(000) = 1420, μ = 0.498 mm-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I > 2σ(I). The title complex has a {[Mn(H2BPTC)(tpy)(H2O)]}n chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π···π, C-H···π and rich hydrogen bonds to form a metal-organic coordination polymer.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

Synthesis and Characterization of Two Mononuclear Mn~Ⅲ Compounds with Mixed Schiff Base Ligands

Two mononuclear Mn compounds of Mn III (salen)(L 1) and Mn III (salen)(L 2) (H 2 salen=N,N-ethylenebis-(salicylideneaminato),L 1=4-(2-hydroxybenzylideneamino)benzoic acid and L 2=4-(2-hydroxybenzylideneamino)-2-hydroxybenzoic acid) have been prepared and characterized by X-ray crystallography.Both compounds crystallize in the monoclinic system,space group P2 1 /c with a=14.351(4),b=14.955(3),c=11.869(3) and β=91.529(3)° for 1;and those for 2:a=14.439(9),b=15.217(9),c=11.660(7) and β=91.648(1)°.The compounds have similar structures,in which the Mn III center adopts a distorted square-pyramidal geometry with the basal plane constructed by two N and two O atoms from the salen ligand and the apical position occupied by the carboxylate O atom from L 1 or L 2 ligand.The voltammetric behavior of the compounds is examined,which shows quasi-reversible one-electron reduction of Mn(Ⅲ) to Mn(Ⅱ).The reduction potentials of both compounds fall between-0.33 V [E 0 (O 2 /O 2 ·)] and 0.65 V [E 0 (1 O 2 /O 2 ·)],which suggest that 1 and 2 could be potential mimics of Mn-SOD.     

N,N''-亚乙基双(1-苯基-3-亚氨基-1-丁酮)硫氰酸根合锰(Ⅲ)的合成和晶体结构

合成了N,N”-亚乙基双(1-苯基-3-亚氨基-l-丁酮)硫氰酸根合锰(Ⅲ),Mn(C_(22)H_(22)·N_2O_2)(NCS),M_r=459.44.该配合物晶体的晶体学参数为:三斜晶系,P1空间群,a=1.0702(3),b=1.2342(2),c=0.8999(2)mm,a=93.74(2)°β=97.09(2)°γ=109.07(2)°,V=1.1078(9)nm~3,D_c=1.377g·cm~(-3),Z=2,F(000)=476,μ=6.85cm~(-1)晶体结构用直接法解出,3205个I≥4σ(I)的可观测点用于结构修正,最终R=0.052,R_w=0.067 Mn原子由三个N原子和两个O原子形成扭曲的四角锥配位构型,晶体沿C轴方向存在贯穿整个晶体的空“隧道”.红外光谱和拉曼光谱均表明配体在形成配合物后,vC=N,vC=O和vC=c带均移向低频.vC=N带(2063cm~(-1))表明NCS~-是通过N原子与Mn(Ⅲ)配位.拉曼光谱中,462cm~(-1)和399cm~(-1)分别为Mn—O和Mn—N的振动带.电子光谱表明有d～d~*,π～π~*跃迁和d～π~*荷移跃迁.电极电位测定表明该配合物中Mn(Ⅲ)不易被氧化和还原.并进行了量化计算     

[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O的 合成、晶体结构及磁性质

Mn(O2CMe)2·4H2O、咪唑、苯甲酸和N(n-Bu)4MnO4在无水乙醇溶剂中反应,制备得到锰的三核μ3-O桥联配位化合物[Mn3O(O2CC6H5)6(C3H4N2)3]·C6H5CO2·0.5H2O.该配位化合物的X射线单晶衍射表明,其属于单斜晶系,空间群P21/C,晶胞参数：a=1.52832(19)nm,b=1.9722(2)nm,c=2.1023(3)nm,β=92.597(3)°,Z=4.变温磁化率(5～280K)研究表明,该配位化合物中3个锰离子在低温下存在弱的反铁磁性耦合,交换积分J=-2.34cm^-1。     

具有非正规自旋态结构的新型Mn(Ⅱ)-Cu(Ⅱ)-Mn(Ⅱ)三核配合物的合成和磁性

合成和表征了四种新的异三核配合物,{[Mn(L)_2]_2[Cu(Pba)]}(ClO_4)_2,其中Pba表示为亚丙基-1,3-双(草胺酸根);L表示1,10-菲咯啉(phen)、5-硝基-1,10-菲咯琳(NO_2-phen)、2,2’-联吡啶(bpy)、4,4′-二甲基-2,2’-联吡啶(Me_2bpy).基于{[Mn(phen)_2]_2[Cu(pba)]}(ClO_4)_2·H_2O的变温磁化率测量(4.2～300K),求出交换积分J=-41.5cm(-1),表明Mn(Ⅱ)和Cu(Ⅱ)离子间为反铁磁耦合.在 X_MT-T图上,X_MT在175K附近呈现出一极小值,这是具有非正规自旋态结构的多金属耦合体系的典型特征.     

Syntheses and Crystal Structures of Copper（Ⅱ） and Nickel Complexes with 1,2,3-Triazole-carboxylic Acid

Three novel complexes [Cu(L1)2(H2O)2] (1), [Ni(L1)2(H2O)2]·(H2O)4(2,HL1=5-methyl-1-(4-methylphenyl)-1,2,3-triazole-4-carboxylic acid) and [Ni2 (HL2)2(CH3OH)6]·(CH3OH)2(3,H3L2=1,2,3-triazole-4,5-dicarboxylic acid) were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1 and 2 are mononuclear structures, and are assembled into a two-dimensional sheet by C(7) H(7)···O(3) weak interactions or hydrogen-bonding interaction. Complex 3 is a centrosymmetric dinuclear structure, and is assembled into a three-dimensional supramolecular structure by hydrogen-bonding interaction.     

Hydrothermal Synthesis and Crystal Structure of a New Polyoxovanadate:[Mn(en)_3]_2en_(0.5)[HV_8~ⅤV_8~ⅣO_(38)(Cl)]·4.5H_2O(en=Ethylenediamine)

A new compound has been synthesized under hydrothermal conditions and characterized by IR,elemental analysis,XPS and single-crystal X-ray diffraction analysis. The title compound [Mn(en)3]2en0.5[HV16O38(Cl)]·4.5H2O crystallizes in monoclinic,space group C2/c,with a=17.016(4),b=18.858(4),c=18.872(4),β=93.667(4)o,V=6043(2)3,Z=4,Dc=2.242 g/cm3,Mr=2040.12,F(000)=4020,μ=2.895 mm-1,Rint=0.0921,R=0.0649 and wR=0.1325. Single-crystal X-ray structure analysis indicates that the title compound consists of a polyanion [HV8VV8IVO38(Cl)]4-cage,two [Mn(en)3]22+ cations,four and a half lattice waters and a half ethylenediamine. In addition,intermolecular O-H···N,O-H···O,N-H···O and C-H···O hydrogen bonds link the molecules together to form a three-dimensional structure.     

夹心型锰杂多配合物作为磁共振成像造影剂的研究

以两种夹心型锰杂多配合物K10[Mn4(PW9O34)2]·22H2O和Na16[Mn4(H2O)2(P2W15O56)2]·53H2O作为研究对象, 采用元素分析和红外光谱对其结构进行了表征, 测试其在水中、牛血清白蛋白及运铁蛋白溶液中的弛豫效率, 并进行了大鼠活体成像实验. 结果表明, 这两种锰杂多配合物的弛豫效率高于或接近于目前临床常用的造影剂Gd-DTPA, 对肝脏和肾脏MRI信号具有良好的增强效果, 是比较好的潜在磁共振成像造影剂候选化合物.     

混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能

[Mn3O(O2CCH2Cl)6(C5H5N)2(H2O)]· CH2ClCOO· H2O在 pH=4.5的 HOAc NaOAc的缓冲水溶液中和 2,2′联吡啶 (bipy)反应,制得了混合价双核锰配合物 [(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3· 1.5H2O。该配位化合物的 X射线单晶衍射表明,该晶体属单斜晶系,空间群 P21/c,晶胞参数： a=1.3854(3), b=1.3943(3), c=2.4225(5)nm,β =103.30°, V=4.554(2)nm3, Z=4, Dc=1.448g· cm－ 3。其紫外可见光谱在 640nm处有一个峰,可指派为桥配体 O2－到 Mn?的电荷迁移光谱 .循环伏安实验说明,此配合物在半波电位 E1/2为 1.25V处,有一个可逆的氧化还原峰,这相应于 (Ⅲ, Ⅳ )态氧化为 (Ⅳ,Ⅳ )态 ,另外在 0.37V处有一阴极峰,相应于 (Ⅲ,Ⅳ )态还原为 (Ⅲ,Ⅲ )态,在 0.81V处有一氧化峰,相应于 (Ⅲ,Ⅲ )态氧化为 (Ⅲ,Ⅳ )态,这两个峰是不可逆的。     

四核Mn(Ⅳ)配合物[L_4Mn_4O_6](ClO_4)_4·2H_2O的合成、结构及磁性研究

近年来 ,由于在金属蛋白中发现氧桥联锰配合物的结构单元[1～ 3] ,对这类配合物的研究更加受到人们的重视 .多核锰配合物的化学研究也随着新型无机材料的发展而引起人们更大的兴趣 [4 ] .本文以大环配体 tacn(即 1 ,4,7-三氮杂环壬烷 )为端基配体 ,合成了四核 Mn( )配合物 [L4 Mn4 O6]( Cl O4 ) 4 ·2 H2 O,并对其结构及性质进行了研究 .1　配合物的合成将 0 .1 2 9g( 1 mmol) tacn[5,6]配体溶于 2 0 m L甲醇中 ,加入到 0 .2 4 5 g( 1 mmol) Mn( CH3COO) 2 ·4H2 O的 1 0 m L水溶液中 ,于室温下搅拌 5 h后得到深蓝色溶液 .再加入 0…     

Synthesis and Structure Characterization of a Tetranuclear Manganese(Ⅲ) Complex:[Mn_4O_2(O_2CMe)_6(MeOH)_2(dbm)_2]·2MeCOOH·2CH_2Cl_2

The title compound, [Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2 (Hdbm = dibenzoylmethane), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P1, with a = 10.729(3), b = 12.269(3), c = 13.085(4) , α = 106.367(3), β = 107.643(2), γ = 94.771(2)o, V = 1547.9(7) 3, Z = 1, C50H64Cl4Mn4O24, Mr = 1410.57, Dc = 1.513 g/cm3, F(000) = 724, Rint = 0.0147, T = 293(2) K and μ = 1.046 mm–1. The final R = 0.0359 and wR = 0.0938 for 5791 observed reflections with I > 2σ(I). The structure of the complex consists of one [Mn4(μ3-O)2]8+ core with four coplanar Mn atoms disposed in an extended “butterfly-like” arrangement and two O atoms triply bridging each “wing”, and the peripheral ligation is provided by six μ2-MeCO2– , two terminal μ2-dbm– groups at the two ends of the molecule, and two MeOH molecules on the central Mn atoms. Intermolecular O…H–O hydrogen bonding interactions are found within the structure of the compound.     

由Mn2+连接仲钨酸盐[H2W12O42]10-构成一维梯型链状多金属氧酸盐

利用Na2WO4·2H2O与MnCl2反应, 合成了一个结构新颖的一维梯型链状的多金属钨酸盐K6[Mn2(H2O)8(H2W12O42)]·14.5H2O(1), 并通过元素分析、红外光谱、热重分析、紫外光谱、电化学和X射线单晶衍射对其进行了表征. 结果表明, 该化合物属于单斜晶系, P2(1)/n空间群，晶胞参数a=1.5042(3) nm, b=1.0462(2) nm, c=1.8843(4) nm, β=93.55(3)°, V=2.9594(10) nm3, Z=2. 该化合物具有由同多酸盐和Mn2+离子构筑的一维梯型链状结构.     

水杨醛苯甲酰腙锰配合物的研究

水杨醛苯甲酰腙C_(14)H_(12)O_2N_2(H_2L)常作为三齿配体和金属离子配位,有两种不同配位形式:HL~-(只失去酚羟基质子)和L~(2-)(进一步失去胺基原子)。本文用以合成了下列两种不同价态锰的配合物:Mn(Ⅱ)(HL)_2和Mn(Ⅲ)(HL)L以及Mn(Ⅱ)(HL)(CH_3COO)·1.5H_2O和Mn(Ⅲ)L(CH_3COO)·0.5H_2O,迄今文献中只见Mn(Ⅱ)L和Mn(Ⅲ)LX(X=CH_3COO~-、Cl~-、Br~-)型双核锰配合物的研究报道。     

Cu(Ⅱ)-氨基酸-核苷酸三元配合物——Ⅱ.Cu(Ⅱ)—L-组氨酸、L-赖氨酸-5′-嘌呤核苷酸三元配合物

合成和表征了新的三元配合物:[Cu(L-His)(5′-AMP)]Cl_2·4H_2O,[Cu(L-His)(5′-GMP)]Cl_2,[Cu(L-His)(5′-IMP)]Cl_2·2H_2O,[Cu(L-Lys)_2(5′-GMP)]Cl_2·6H_2O,Na_2[Cu(L-Lys)_2(5′-GMPH_(-2)]·6H_2O,Na_2[Cu(L-Lys)_2(5′GTP_(-2))]·6H_2O,Na_2[Cu(L-Lsy)_2(5′-IMPH_(-2))]·10H_2O.IR及NMR谱表明,5′-嘌呤核苷酸以嘌呤碱基上的7-N原子与Cu(Ⅱ)配位.在5′-嘌呤核苷酸形成的配合物中,磷酸根不参与配位,但是Na_2·5′-GMPH_(-2)和Na_2·5′-GTPH_(-2)的磷酸根参与配位,而Na_2·5′-IMPH_(-2)的磷酸根不参与配位.