Hydrothermal Syntheses and Crystal Structures of Cobalt（Ⅱ） Complexes Constructed by Dipyrido[3,2-a：2＇,3＇-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2(bptc)(DPPZ)2(H2O)2]·H2O}n 1 and {[Co2(ccm)2(DPPZ)2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co(NO3)2·6H2O with chelating ligand dipyrido[3,2-a:2',3'-c]phenazine(DPPZ) and the corresponding carboxylic acid,namely,3,3',4,4'-benzophenonetetracarboxylic acid(H4bptc) or 2-carboxycinnamic acid(H2ccm),respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.     

由羧酸配体和铁(Ⅱ)构筑的两个过渡金属配位聚合物的结构、表征和性质（英文）

采用水热法合成了2个铁的过渡金属配位聚合物[Fe(Medpq)(BDC)H2O]n(1)和{[Fe(Medpq)(QUI)H2O]·2H2O}n(2)(Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline;H2BDC=terephthalic acid;H2QUI=2,3-pyridinedicarboxylic acid),并对其进行了元素分析、红外光谱和热重表征,并用X射线单晶衍射测定结构。2个配位聚合物中的中心铁(Ⅱ)离子,都呈现一个稍微扭曲的八面体几何构型。     

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.     

Structures of 1-（3,4-Dihydroxyphenyl）-2-（3,4-dimethoxyphenyl） ethanone and Its Hydrate Complex

The title compounds, C16H16O5 (I) and C16H16O5·H2O (II), were structurally characterized by single-crystal X-ray diffraction. Compound I crystallizes in monoclinic space group P21/c with a = 10.5574(10), b = 8.3576(9), c = 16.5528(16) , β = 91.762(3)°, Z = 4, R = 0.0524 and wR = 0.1084. The molecules are jointed into a chain by intermolecular O-H···O and C-H···O hydrogen bonds, which form layers parallel to (001). The chains run along the [110] and [110] directions alternatively layer by layer, and are assembled into a network by intermolecular O-H···O (carboxyl) hydrogen bonds. On the other hand, the hydrate complex (II) crystallizes in the triclinic space group P1 with a = 5.1451(2), b = 10.4583(4), c = 14.8267(5) , α = 70.900(2), β = 82.478(2), γ = 81.359(2)°, Z = 2, R = 0.0393 and wR = 0.0983. The molecules are linked into infinite two-dimensional ribbons by O-H···O (carbonyl) and solvent-bridged O-H···O hydrogen bonds.     

Syntheses and Crystal Structures of Two Octamolybdate Compounds Modified by CuⅡ-Imidazole Cations

Two new polyoxomolybdate compounds,namely(CuIIL2)2[CuⅡ(HL)2]2[Mo8O26(HL)2].(H2O)4(1) and [CuⅡ(HL)2]2[β-Mo8O26](HL)2(2)(HL=imidazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one Mo8O26(HL)24-cluster,two CuL2,two Cu(HL)22+,and four disassociated water molecules;and compound 2 is constructed by one β-Mo8O264-cluster,two Cu(HL)22+,and two uncoordinated imidazole molecules.     

Synthesis,Structure,Fluorescent Property and Natural Bond Orbital（NBO） Analysis of a One-dimensional Cobalt（III） Complex Containing 1,3-Benzenedicarboxylate and 2-Methyldipyrido[3,2-f：2＇,3＇-h]quinoxaline Ligand

A novel metal-organic coordination polymer [Co(m-BDC)(Medpq)·2H2O]n(m-H2BDC = benzene-1,3-dicarboxyalic acid,Medpq = 2-methyldipyrido[3,2-f:2',3'-h]quinoxaline) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction.The title compound crystallizes in monoclinic,space group C2/c with a = 19.986(4),b = 15.789(3),c = 16.292(3),β = 126.54(3)°,V = 4130.3(14)3,C23H18N4O6Co,Mr = 505.34,Dc = 1.625 g·cm-3,Z = 8,μ = 0.883 mm-1,F(000) = 2072,the final R = 0.0772 and wR = 0.1428.The crystal structure of complex 1 is an infinite zigzag-like chain of hexacoordinate Co3+ ions,in which the Co3+ ions are bridged in two coordination modes by m-BDC2+ ligands and decorated by Medpq ligands,showing a slightly distorted octahedral geometry.Additionally,the compound shows strong fluorescence in the solid state at room temperature.Natural bond orbital(NBO) analysis is performed by using the NBO method built in Gaussian 03 Program.The calculation results show a covalent interaction between the coordinated atoms and Co3+ ions.     

Hydrothermal Synthesis and Structure of [CH_3NH_3]_2[(V~ⅣO)_2(V~ⅤO_4)_2]: A New Layered Mixed-valence Vanadium Oxide Incorporated with Organic Cations

IntroductionLayered intercalation compounds haveattracted increasing research attention due to theirapplications in diverse areas,for instance,some ofthem are used as rechargeable batteries,heterogeneous catalysts,and an exchange[1— 12 ] . Inprevious literatures,several layered mixed- valencevanadium oxides were reported,such as VO2 · 1 /2 H2 O[13 ] ,[H2 N( CH2 ) 4 NH2 ]V4O9[14 ] ,NH4V3 O8[15] ,( C6H14 · N2 ) V6O14 · 1 / 2 H2 O[16] ,[HN( C2 H4) 3 NH]V6O14 [17] ,NMe4V6O14 [18]…     

[Cu(bpp)2(bpdc)(H2O)2]×2H2O and [Cu(bpp)2](tdc)×7.5H2O的合成、晶体结构和热稳定性

在室温下, 由Cu(NO3)2 、1,3 -二（4 -吡啶基）丙烷(bpp)、4,4 ’ -联苯二甲酸(H2bpdc)和2,5-噻吩二甲酸(H2tdc)制备出两种新型铜( II)配位聚合物[Cu(bpp)2(bpdc)(H2O)2]n·2nH2O, 1 和[Cu(bpp)2]n·n(tdc) 7.5nH2O, 2。两个配位聚合物均为一维线型结构,铜原子均采取变形的八面体结构,在轴线方向上的两个水分子与铜原子存在较弱的配位作用。在配合物1中,两个bpdc羧酸根离子与铜原子配位,而2中的tdc羧酸离子没有与铜原子键合,只是作为反离子平衡电荷。在两个产物中, 配体bpp具有不同的构象。热重分析表明配合物1与2分别在110°C和160°C以下是稳定的。     

Low temperature heat capacities and thermodynamic properties of rare earth triisothiocyanate hydrates——Pr(NCS)_3· 7H_2O and Nd(NCS)_3· 7H_2O

Heat capacities of Pr(NCS)3·7H2O and Nd(NCS)3· 7H2O haw been measured from 13 to 300 K by using a fully automated adiabatic calorimeter. Schottky anomaly was observed for Pr(NCS)3·7H2O below 50 K. The polynomial equations for calculating the heat capacity values of the two compounds in the range of 13-300 K were obtained by the least-squares fitting based on the experimental Cp data. The Cp values below 13 K were estimated by using the Debye-Einstein and Schottky heat capacity functions. The standard molar thermodynamic functions were computed from 0 to 300 K. The standard entropies and Gibbs energies of formation of the two compounds were also calculated.     

Synthesis and Crystal Structure of Two Coordination Complexes Based on H2dpa and Tmd Ligands

Two new transition metal compounds, [Mn(dpa)2(tmd)2]n (1, H2dpa = 4-hydroxy-phenyl-acetic acid, tmd = 4,4-trimethylenedipyridine) and [Co4(dpa)6(tmd)4(H2O)4]n·nH2O·nCl2 (2), have been synthesized by hydrothermal synthesis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.828(3), b = 17.493(5), c = 11.616(4), β = 110.146(6)o, V = 1874.9(10)3, C42H42MnN4O6, Mr = 753.74, Z = 2, Dc = 1.335 g/cm3, μ = 0.406 mm–1, F(000) = 790, the final R = 0.1047 and wR = 0.2021 for 2698 observed reflections (I > 2σ(I)). Compound 2 crystallizes in the monoclinic system, space group P21/c with a = 11.7214(13), b = 17.1582(19), c = 24.625(3), β = 103.055(3)o, V = 4824.4(9)3, C100H104Cl2Co4N8O23, Mr = 2094.55, Z = 2, Dc = 1.443 g/cm3, μ = 0.809 mm–1, F(000) = 2180, the final R = 0.0550 and wR = 0.0673 for 4104 observed reflections (I > 2σ(I)). These complexes were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. The structural analyses show that the two compounds are both one-dimensional chain structures. However, compounds 1 and 2 form threedimensional supramolecular structures by hydrogen bonds, respectively.     

以邻苯二甲酸根及邻菲咯啉衍生物构筑的锰配位聚合物的合成、晶体结构及磁性

采用水热法合成了一个配位聚合物{[Mn(Pht)(Medpq)(H2O)].0.25nH2O}n(Pht=phthalate,Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline)1,并对其进行了元素分析、红外光谱、热重表征、磁性表征和X射线单晶衍射测定。配位聚合物1属于单斜晶系,空间群为P21/c。晶胞参数为:a=1.5980(3)nm,b=2.0925(4)nm,c=0.65967(13)nm,β=93.06(3)°,V=2.2027(8)nm3。在晶体中,锰原子与4个氧原子和2个氮原子形成六配位的畸变的八面体构型。整个晶体由Pht-Mn-Medpq单元组成一维双链结构。     

配合物[Ni(Pht)(Medpq)(H2O)3]n的水热合成、表征及自然键轨道(NBO)分析

采用水热法合成了一种新型金属配合物[Ni(Pht)(Medpq)(H2O)3]n(1)(Pht=phthalic acid,Medpq=2-methyldipyrido[3,2-f∶2′,3′-h]quinoxaline),并对其进行了元素分析、红外光谱、热重表征、X射线单晶衍射测定和理论计算。在晶体中,Ni(Ⅱ)与来自于Medpq分子上的2个氮原子,邻苯二甲酸上的1个氧原子及来自于3个不同的配位水分子上的3个氧原子配位,形成畸变的八面体构型。整个晶体由Pht-Ni-Medpq单元组成零维结构。应用Guassian03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道(NBO)进行了分析,结果表明Ni(Ⅱ)与配位原子间的价键类型都属于共价键范畴。     

2-(N，N-二羧甲基氨甲基)氢醌金属配合物(钴、镍、锌)的合成、晶体结构及电化学性质研究

合成了3个新的氢醌金属配合物:[Co(H2cah)(H2O)2].H2O(1),Ni(H2cah)(H2O)2].H2O(2),[Zn(H2cah)(CH3OH)(H2O)].H2O(3)(H4cah=2-(N,N-二羧甲酸氨甲基)氢醌),通过X-射线单晶衍射,红外光谱,元素分析对它们进行了表征。这些配合物均为单核结构,并且通过分子间的氢键形成了无限的超分子网状结构。电化学研究显示配合物1中的Co2+/Co+对和配合物2中的Ni2+/Ni+对的氧化还原是一个不可逆的过程,但是氢醌到半醌之间的转换是一个准可逆的过程。     

Polyoxometalate-templated lanthanide-organic hybrid layers based on 6(3)-honeycomb-like 2D nets

The reaction of a double-betaine-containing ligand with LnPMo(12)O(40)·nH(2)O (Ln = Dy, Tb and Er) led to the isolation of new polyoxometalate-templated lanthanide-organic hybrid layers with the molecular formula [Ln(L)(1.5)(H(2)O)(5)][PMo(12)O(40)]·1.5CH(3)CN·2H(2)O (Ln = Dy (1), Tb (2) and Er (3); L = 1,4-bis(pyridinil-4-carboxylato)-l,4-dimethylbenzene). All compounds were characterized by elemental analyses, TG analyses, IR and the single-crystal X-ray diffraction. Compounds 1-3 are isostructural and possess a 2D undulating cationic network [Ln(L)(1.5)(H(2)O)(5)](n)(3n+) with the honeycomb-like cavities. Interestingly, the interval 2D networks are further connected by the H-bonds to form a 3D supramolecular framework. Moreover, two of such identical supramolecular frameworks are 2-fold interpenetrated with each other and encapsulate the α-Keggin-type [PMo(12)O(40)](3-) anionic templates and the solvent molecules. These composite compounds display both luminescent properties (induced by organic ligands and/or lanthanide ions) and electrocatalytic activities towards the reduction of nitrite.     

Syntheses, characterization, and magnetic studies of copper(II) complexes with the ligand N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine (1,3-tpbd) and its phenol derivative 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresol] (2,6-Htpcd)

The copper(II) complexes [Cu(4)(1,3-tpbd)(2)(H(2)O)(4)(NO(3))(4)](n)(NO(3))(4n)·13nH(2)O (1), [Cu(4)(1,3-tpbd)(2)(AsO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (2), [Cu(4)(1,3-tpbd)(2)(PO(4))(ClO(4))(3)(H(2)O)](ClO(4))(2)·2H(2)O·0.5CH(3)OH (3), [Cu(2)(1,3-tpbd){(PhO)(2)PO(2)}(2)](2)(ClO(4))(4) (4), and [Cu(2)(1,3-tpbd){(PhO)PO(3)}(2)(H(2)O)(0.69)(CH(3)CN)(0.31)](2)(BPh(4))(4)·Et(2)O·CH(3)CN (5) [1,3-tpbd = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-benzenediamine, BPh(4)(-) = tetraphenylborate] were prepared and structurally characterized. Analyses of the magnetic data of 2, 3, 4, and [Cu(2)(2,6-tpcd)(H(2)O)Cl](ClO(4))(2) (6) [2,6-tpcd = 2,6-bis[bis(2-pyridylmethyl)amino]-p-cresolate] show the occurrence of weak antiferromagnetic interactions between the copper(II) ions, the bis-terdentate 1,3-tpbd/2,6-tpcd, μ(4)-XO(4) (X = As and P) μ(1,2)-OPO and μ-O(phenolate) appearing as poor mediators of exchange interactions in this series of compounds. Simple orbital symmetry considerations based on the structural knowledge account for the small magnitude of the magnetic couplings found in these copper(II) compounds.     

基于柔性1，4-苯二硫乙酸和刚性的2，2′-联吡啶配体构筑的钴配合物的合成、晶体结构及电化学性质

水热法合成了2个基于柔性的1,4-苯二硫乙酸(H2L)和刚性的2,2′-联吡啶(2,2′-bipy)配体的Co(Ⅱ)配合物:{[CoL(2,2′-bipy)(H2O)].0.40H2O}n(1)和[CoL(2,2′-bipy)(H2O)2]n(2),并通过元素分析,红外光谱,热重和X-射线单晶衍射实验对其结构进行了表征。分析表明,两个配合物都是通过氢键连接一维链形成的二维层面结构。对配合物的电化学性质进行了研究,表明两个配合物有相似的电化学行为。     

1,2,4-苯三甲酸铜二维网状配合物的合成及结构表征(英)

在室温下,MnSO₄·H₂O和1,2,4-苯三甲酸(H₃BTC)反应得到化合物[Mn(H₂BTC)₂(H₂O)₄]·2H₂O (1),化合物1和CuSO₄·5H₂O反应得到化合物[Cu(HBTC)(H₂O)_1.5]·H₂O (2)。化合物1是一个单核分子化合物。在化合物1中,每个锰离子和两个H₂BTC^－离子及四个水分子配位。化合物2中,每个铜离子和三个HBTC^2－及两个水分子配位,其中的一个水分子起桥联作用从而形成二维网状结构。     

Synthesis, Crystal Structure and Luminescent Property of a Novel 1-D Cadmium(Ⅱ) Complex: [Cd2(C8H3NO6)2(H2O)4]n·2nH2O

A novel one-dimensional chain-like coordination polymer constructed from 3-nitrobenzene-1,2-dicarboxylic acid, [Cd2(C8H3NO6)2(H2O)4]n·2nH2O, has been synthesized and its structure was determined by X-ray crystallography method. The crystal belongs to monoclinic, space group P21/c with a = 6.1252(8), b = 20.706(3), c = 8.8067(11) (A), β = 95.608(2)°, V= 1111.6(2)(A)3, Mr =751.12, Dc = 2.244 g/cm3, F(000) = 736, μ = 2.011 mm-1, Z = 2, the final R = 0.0262 and wR = 0.0692for 2338 observed reflections with I ＞ 2σ(I). The structure of the title compound presents a 1-D chain-like structure constructed by dimer units, [Cd2(CsH3NO6)2(H2O)4]n, through two carboxylate oxygen atoms. The fluorescence of the tifle compound has been also discussed in this paper.     

Hydrothermal synthesis, structure, and luminescent properties of selected Zn(II)/Cd(II) coordination polymers constructed from 3,5-bis(x-pyridyl)-1,2,4-triazole (x = 3, 4)

Utilizing 3,5-bis(x-pyridyl)-1,2,4-triazole (x-Hpytz, x = 3; x = 4) as multidentate ligands, six novel coordination polymers with Zn(II) or Cd(II) metal ions were prepared: [Zn(3-pytz)(0.5)(OH)(0.5)Cl](n) (1, 1D ladder), {[Zn(3-Hpytz)(H(2)O)(4)] [Zn(3-Hpytz)(H(2)O)(3)·SO(4)]SO(4)·5H(2)O}(n) (2·5H(2)O, 1D chain), [Cd(3-Hpytz)(SO(4))](n) (3, 3D framework), {[Cd(3-Hyptz)SO(4)·3H(2)O]·2H(2)O}(n) (4·2H(2)O, 1D chain), [Zn(4-pytz)Cl](n) (5, 3D framework) and [Zn(2)(4-pytz)(SO(4))(OH)](n) (6, 3D framework). All compounds were obtained from hydrothermal reactions, with the exception of compound 4 which was obtained by solvent diffusion at room temperature. All compounds were characterized by FTIR, elemental analysis and TGA analysis and their structures were determined by X-ray diffraction. All compounds exhibited substantial thermal stability and showed photofluorescent properties that resulted from ligand π-π* transition.     

配合物[RE2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]•2H2O的合成、 晶体结构及其与DNA作用方式初探

以N-(2-异丙酸)-邻羟基苯甲酰腙(C10H10N2O4, H3L)、2,6-吡啶二甲酸(2,6-H2PDA)与RE(NO3)3•nH2O (RE＝Pr, Eu)在室温下反应, 合成了配合物1 [Pr2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]•2H2O和配合物2 [Eu2(H2L)2(HL)2(2,6-H2PDA)- (H2O)2]•2H2O, 对其进行了元素分析、红外光谱、紫外光谱等表征, 测定了两种配合物的晶体结构. 通过紫外吸收光谱、荧光发射光谱和稳态荧光猝灭方法及其与溴化乙锭(EB)的竞争实验研究了两种配合物与小牛胸腺DNA的作用情况. 结果表明, 两种配合物与小牛胸腺DNA均是以插入方式结合的.