一维链状锌配位聚合物{[Zn(H2O)2(L)(phen)]·3H2O}n的合成、晶体结构和性能研究

合成了一种锌配位聚合物{[Zn(H₂O)₂(L)(phen)]·3H₂O}_n (1), 其中, H₂L=1-氨基-8-萘酚-3, 6-二磺酸并利用元素分析、红外、紫外、荧光、热重和X-射线单晶衍射分析进行了表征。标题配合物属正交晶系, Pnma空间群, a=1.698 90(12) nm, b=0.661 88(11) nm, c=2.480 40(14) nm, V=2.789 1(5) nm³, Z=4, M_r=634.92, D_c=1.512 g·cm^-3, R=0.058 6, wR=0.121 4。标题配合物呈现一维链状结构, 链内L²-和phen配体之间存在π-π堆积作用, 链与链之间通过氢键扩展为二维超分子网络。     

一维配位聚合物[Cu(2-pac)2·2H2O]n的合成与结构

近年来,配位聚合物由于在光学、电学、磁学、催化、分离及吸附等方面具有潜在的功能性,处于化学、材料、生物、物理等许多学科的交叉点,成为当前最活跃的前沿研究领域之一[1～8],因此进一步合成具有特定结构和功能的配位聚合物具有非常重要的意义和价值[9～12].     

一维链状配位聚合物[Cu3(TFSSB)2·(H2O)4·4H2O]n的合成和晶体结构

The title complex [Cu₃(TFSSB)₂·(H₂O)₄·4H₂O]_n (TFSSB=taurine 3-formylsalicylic schiff base) was synthesized by TFSSB and copper(Ⅱ) acetate monohydrate in ethanol solution and the crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic system, space group P2₁ / n，with cell parameters: a=0.927 9(6) nm, b=1.173 0(2) nm, c=1.471(2) nm, β=106.96(2)°, and V=1.531(2) nm³, Z=2, D_c=1.890 g·cm^-3, μ=2.291 mm^-1, F(000)=882, R₁=0.025 9, wR₂=0.065 9. The Cu1 is five-coordinate, the Cu2 is four-coordinate. CCDC: 253298.     

配位聚合物[Mn(2，4，6-TMBA)2(H2O)3]n·2nH2O的水热合成和晶体结构

The title compound, [Mn(2,4,6-TMBA)₂(H₂O)₃]_n·2nH₂O(1), where 2,4,6-TMBA=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of monoclinic, space group C2/c with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 04(17) nm, V=2.494 7(9) nm³, Z=4, M=471.40, D_c=1.255 g·cm^-3, μ=0.571 mm^-1, F(000)=996, R_int=0.029 4, R=0.037 6 and wR=0.094 9. The Mn atoms are octahedrally coordinated by two O atoms of two ligands and four O atoms of water. The carboxyl group coordinates to Mn(Ⅱ) in the mode of monodentate, while the O atoms of water molecules coordinates in bridging mode. The complex shows a one-dimensional chain structure bridged by water molecules. CCDC: 297750.     

{[Cu4(nip)4(4，4′-bipy)4(DMF)4]·CH3OH}n配合物的合成与晶体结构

A coordination polymer, {[Cu₄(nip)₄(4，4′-bipy)₄(DMF)₄]·CH₃OH}_n, have been synthesized by the layer method using 5-nitroisophthalic acid (H₂nip), Cu(CH₃COOH)₂ and 4,4′-bipyridine(4,4′-bipy) with three solutions in a marrow tube and structurally characterized by X-ray single-crystal structure analysis. The results indicated that the nip ligand has a μ₂ mono-atomic bridging-monodentate coordination mode and the structure is a two-dimensional network. CCDC: 623420.     

一维链状镍配位聚合物{[Ni(DNBC)2(Im)(H2O)]·0.25H2O}n的合成、晶体结构及热学性质研究

在水和乙醇混合溶液中合成了配合物{[Ni(DNBC)2(Im)(H2O)]·0.25H2O}n(DNBC=3,5-二硝基苯甲酸,Im=咪唑),并进行了元素分析、红外光谱、热重分析(TG)对其进行了表征,用单晶X-射线衍射测定了配合物的晶体结构。结果表明此配合物属正交晶系,空间群为Pbca,a=1.5022(6)nm,b=1.5146(6)nm,c=1.9269(7)nm,V=4.384(3)nm3,Z=8,F(000)=2320。配合物中金属镍原子采用五配位,分别与4个氧原子和1个咪唑氮原子配位,形成1个扭曲的四方锥体。     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln2（pda）3（H2O）2]2H2O}n（Ln=Nd/La）

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸（H₂pda）反应得到了2个新颖的稀土配位聚合物{[Ln₂（pda）₃（H₂O）₂]·2H₂O}_n（Ln=Nd（1）,La（2））。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1：a=2.62906（18）nm,b=1.61172（11）nm,c=0.78327（5）nm,β=93.173（5）°,V=3.3139（4）nm³,Z=4,F（000）=1840,μ=3.173mm^-1,D_c=1.878g·cm^-3,R₁=0.0226,wR₂=0.0609;配合物2：a=2.6271（14）nm,b=1.6149（8）nm,c=0.7966（4）nm,β=92.850（9）,V=3.375（3）nm³,Z=4,F（000）=1816,μ=2.570mm^-1,D_c=1.823g·cm^-3,R₁=0.0466,wR₂=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

配位聚合物{[Co(4,4′-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

The complex {[Co(4,4′-bpy)(H₂O)₄](Fum)·4H₂O}_n(where 4,4′-bpy = 4,4′-bipyridine and Fum = fumarate) was synthesized and characterized by X-ray diffraction. The complex consists of one-dimensional chains containing cobalt(Ⅱ) ions bridged by 4,4′-bpy molecules. The six-coordination of Co²⁺ is achieved by means of four water molecules. The fumarate is not coordinated to cobalt ion while it forms hydrogen bonds with coordinated and non-coordinated water molecules and extends the structure into three-dimensional hydrogen bonding network. CCDC: 190488.     

一维链状的2-氧-1(4H)-吡啶氮乙酸钴配位聚合物{[Co(2-OPA)2(4，4′-bipy)(H2O)2]·6H2O}n的合成、结构及性能研究

A coordination polymer of {[Co(2-OPA)₂(4，4′-bipy)(H₂O)₂]·6H₂O}_n (2-OPA^-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis， IR， TG， fluorescence and X-ray single crystal diffraction. The title complex crystallizes in triclinic space group P1， with a=0.856 66(17) nm， b=0.859 58(17) nm， c=1.142 2(2) nm， α=69.64(3)°， β=68.35(3)°， γ=74.88(3)°， and V=0.724 4(3) nm³， Z=1， R=0.064 4， wR=0.159 8. Each Co atom occupies a special position of inversion center and has an octahedral coordination environment， defined by two carboxyl O atoms from two 2-OPA^- ligands， two N atoms from two 4，4′-bipy ligands and two water molecules. Adjacent Co(Ⅱ) atoms are bridged by 4，4′-bipy ligands， forming a one-dimensional linetype chain structure. The closest Co…Co distance is 1.142 2(2) nm. The results of TG and fluorescent analysis show that the title coordination polymer is stable under 90.2 ℃ and has three emission peaks at 368， 422 and 484 nm. CCDC: 643626.     

一维交替链状稀土配位聚合物[Er(dpa)(pya)(H2O)]n和[Nd2(pya)6(H2O)4]n的水热合成及结构表征

在水热条件下，稀土氧化物与2，2′-联苯二甲酸及异烟酸反应得到了两个新颖的一维交替链状配位聚合物[Er(dpa)(pya)(H₂O)]_n和[Nd₂(pya)₆(H₂O)₄]_n(H₂dpa=2，2′-联苯二甲酸；Hpya=异烟酸)。测定了它们的晶体结构，并进行了红外光谱和元素分析等 性质的表征。晶体结构测定表明这两个化合物同属单斜晶系，并具有相同的空间群P2₁/n， 晶体学参数分别为配合物1：a= 0.8830(3) nm，b=1.058 5(3) nm，c=2.089 1(6) nm，β=98.429(4)°，D_c=1.883g·cm^-3， V=1.931 4(10) nm³，Z=4； 配合物2：a=0.968 9(4) nm，b=1.978 3(9) nm，c=1.164 2(6) nm，β=112.106(7)°，D_c=1.756 g·cm^-3，V=2.067 5(17) nm³，Z=4。     

具有一维孔道的配位聚合物[{NaCd4(IDC)3(prz)}·3H2O]n的合成、晶体结构及性质研究

通过水热方法,采用H3IDC(H3IDC=imidazole-4,5-dicarboxylic acid)、prz(prz=piperazine)与Cd(NO3)2·4H2O反应,合成了具有一维孔道的配位聚合物[{NaCd4(IDC)3(prz)}·3H2O]n(1),并对其结构和荧光性质进行了研究.结构分析结果表明该化合物属于单斜晶系,Cc空间群.其结构单元中含有4个独立的Cd原子.3个Cd原子形成一个小环,6个Cd原子形成一个大环.这些环通过IDC<'3->和Cd(Ⅱ)的配位作用,进一步连接产生了含一维孔道的配位聚合物.孔道内含有大量水分子和Na+离子.研究表明,该配合物在室温下能发出很强的兰色荧光.     

2-苯并咪唑苯基膦酸的金属有机膦酸化合物[Mn(2-bppH2)2(H2O)]n和[Cu(2-bppH2)2]·xCH3OH的合成、结构及性质研究

本文报道了两个2-苯并咪唑苯基膦酸(2-bppH3)的过渡金属配合物,[Mn(2-bppH2)2(H2O)]n(1)和[Cu(2-bppH2)2].xCH3OH(2)。化合物1中Mn原子通过O-P-O桥联形成一维链状结构,而化合物2则为单核结构,单核单元之间通过氢键和π-π相互作用形成三维结构。在化合物1中,O-P-O桥联的2个锰离子之间存在反铁磁性相互作用。     

多孔配位聚合物{[Cd2（tpom）（tpa）2]·（DMF）（H2O）3}n的合成及表征

由四(4-吡啶氧甲基)甲烷(tpom)和对苯二甲酸(tpa)与Cd(NO3)2.4H2O合成了配位聚合物{[Cd2(tpom)(tpa)2].(DMF)(H2O)3}n,通过元素分析、红外光谱、X-射线粉末衍射、热重、X-射线单晶衍射对配位聚合物的结构进行了表征。结果表明,标题化合物属于单斜晶系C2/c空间群,晶胞参数为a=3.4747(17)nm,b=2.0899(10)nm,c=1.4292(10)nm,β=111.642(5)°,V=9.647(9)nm3,Z=8,Dc=1.374 g.cm-3,F(000)=3984.0,μ=0.939 mm-1,其6586个可观测点的结构偏差因子R1=0.0566,wR2=0.1408。结构分析表明,对苯二甲酸连接镉离子形成含双核镉(CdCOO)2的平面,四(4-吡啶氧甲基)甲烷连接双核镉形成具有两重穿插pcu拓扑构型的三维骨架。     

一维聚合物{[Co(N3)2(dps)2]·0.5H2O}n的合成，结构和磁性质

A coordination polymer {[Co(N₃)₂(dps)₂]·0.5H₂O}_n (1) (dps=dipyridin-4-ylsulfane) with one dimensional chains has been synthesized and the structure and magnetic properties were characterized. Complex 1 crystallizes belongs to monoclinic system and has space group P2₁/c. The Co^Ⅱ ion is six-coordinated and located at a compressed octahedral environment due to the Jahn-Teller effect. The ligand of dps bridges between Co^Ⅱ ions producing the infinite chains of Co…Co along a direction and, interestingly, four pyridyl groups of dps ligands form a propeller-shaped coordination geometry around Co^Ⅱ ion with the same spiral within the chain. These 1D chains are further linked through the hydrogen bonds to generate a 3D supermolecular network. Magnetic studies indicated that complex 1 shows very weak antiferromagnetic coupling between Co^Ⅱ ions in low temperature. CCDC: 769596.     

二维铜配合物{[Cu2(BIPA)2(bpe)2]·H2O}n的合成、晶体结构及磁性

本文以5-溴间苯二甲酸(H2BIPA)、1,2-双(4-吡啶基)乙烷(bpe)和Cu(NO3)2.3H2O水热反应得到了一个配位聚合物{[Cu2(BIPA)2(bpe)2].H2O}n,并用元素分析、红外光谱以及X-射线单晶洐射对其进行了表征。该晶体属三斜晶系,P1空间群。Cu(Ⅱ)离子通过2个BIPA配体桥联形成一维梯状链,再通过bpe配体连接成二维层状结构。变温磁化率显示羧酸桥联的双核铜之间存在弱的反铁磁相互作用。     

配位聚合物[Cd2(BDC)2(obix)2]·H2O的合成、晶体结构和荧光性质

用水热合成方法得到1个新的配位聚合物[Cd2(BDC)2(obix)2]·H2O(H2BDC=对苯二甲酸,obix=1,2-(二亚甲基)二咪唑).配合物晶体属三斜晶系,P1空间群.晶体结构表明:镉原子与3个对苯二甲酸上的5个氧原子,2个1,2-(二亚甲基)二咪唑中的2个氮原子配位形成扭曲的五角双锥配位构型.2个Cd(Ⅱ)原子通过两个羧基桥联形成一个双核Cd2单元,再通过配体连接成二维层状结构,层与层之间通过C-H…O氢键和弱的π-π相互作用形成三维超分子结构.室温下配合物具有较强的荧光发射光谱.     

发光的二维Cu(Ⅰ)分子箱[CuCl(DBBD)2]n

Hydrothermal treatment of CuCl and atropisomeric ligand racemic-diethyl (R,S)-4,4′-biquinoline-6,6′-diethyl-3,3′-dicarboxylate (DBBD) (1) in the presence of H₂O and C₂H₅OH over 4 days at 104～109 ℃ yielded colorless block crystals [CuCl(DBBD)₂]_n (2). The compound exhibits strong red fluorescent emission with a wavelength of 650 nm. The crystal of [CuCl(DBBD)₂]_n belongs to monoclinic system with space group C2/c, and a=1.656 58(17) nm, b=2.025 0(2) nm, c=1.548 73(16) nm, β=107.879(2)°, V=4.944 4(9) nm³, D_c=1.417 g·cm^-3, Z=8. CCDC: 292932.     

配位聚合物{[Zn(CF3COO)2(C5H5ON)]·H2O}n的合成、晶体结构及表征

new coordination polymer {[Zn(CF₃COO)₂(C₅H₅ON)]·H₂O}_n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C₅H₅ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, ¹H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P2₁/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm³; D_c=2.037 g·cm^-3; Z=2; F(000)=400; μ=1.969 mm^-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.     

二维层状配位聚合物{[Cd(p-CMSP)(Him)(H2O)]·3H2O}n

The novel coordination polymer {[Cd(p-CMSP)(Him)(H₂O)]·3H₂O}_n ( p-CMSP^2-=p-(carboxymethoxy)phenylthioacetate, Him=imidazole) was synthesized by the reaction of Cd(NO3)₂, imidazole and p-(carboxymethoxy)phenylthioacetic acid in an aqueous solution, and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The crystal structure is of monoclinic, space group P2₁/c with a=1.144 0(2) nm, b=1.876 7(4) nm, c=0.877 89(18) nm, β=106.31(3)° and V=1.808 9(7) nm³, Z=4, R=0.023 2, wR=0.051 4. Each Cd(II) atom displays a distorted octahedral coordination geometry, defined by three carboxyl O atoms from different p-CMSP^2- ligands, one S atom from thioether, one N atom from imidazole and one water molecule. Adjacent Cd(II) ions are bridged by p-CMSP^2- groups, resulting in a 2D layer structure. The adjacent Cd…Cd distances are 0.492 7 nm and 1.144 0 nm. Furthermore, such layers are linked through hydrogen bonds to form supramolecular network. CCDC: 269474.     

[{Zn(3-SBA)(2，2′-bipy)(H2O)2}·H2O]n的合成和晶体结构研究

A novel coordination ploymer [{Zn(3-SBA)(2,2′-bipy)(H₂O)₂}·H₂O]_n was synthesized by the hydrothermal reaction of 3-Na₂SBA, ZnSO₄·7H₂O and 2,2′-bipy. The structure was characterized by elemental analysis, IR and single crystal X-ray diffraction. The title coordination ploymer crystallized in monoclinic with space group P2₁, a=0.803 42(18) nm, b=1.501 8(3) nm, c=0.821 13(19) nm, β=109.350(4)°. The coordination polymer has an infinite chain structure and its luminescent property has also been studied. CCDC: 282746.