Synthesis,Crystal Structure and Iodine Capture of a Yttrium(Ⅲ) Coordination Polymer with 5-Aminonicotinic Acid

A new coordination polymer, [（C（18）H（16）N4O（18）Y2）（H2O）]n, has been hydrothermally synthesized by reacting yttrium（Ⅲ） nitrate with 5-aminonicotinic acid and ammonium oxalate at a molar ratio of 1：1：1, and its structure was determined by X-ray crystallography with the following data： monoclinic system, space group C2/c, a = 13.4507（10）, b = 11.5829（9）, c = 16.3448（9） ？, a= 89.983（6）, β = 109.056（6）, g = 90.047（6）°, Z = 4, V = 2406.92（14） ？~3, F（000） = 1536, Dc = 2.13079 g/cm^3, R = 0.0284（1695） and w R = 0.0787（2014）. In the asymmetric unit of the compound, each Y（Ⅲ） ion is bonded to eight oxygen atoms from 5-aminonicotinic acid and oxalate groups and terminal-coordinated water molecule, resembling a highly distorted tricapped trigonal geometry. Adjacent three yttrium atoms are bridged by three identically independent oxalate groups in a side-by-side manner to form brickwall-like 2D sheets, and these sheets are further linked through π-π stacking interactions to generate a 3D supramolecular network. The photoluminescent property of the complex was investigated and the iodine capture studies show that the porous frameworks have reversible absorption ability for iodine molecule.

Synthesis and Structures of Three Erbium(Ⅲ) Dicarboxylate Coordination Polymers

Three polymeric erbium(Ⅲ) complexes [Er(oba)(Hoba)(H 2O) 2]H 2O (A),[Er 2(oba) 3(H 2O) 4] (B), [Er 2(oba) 3(2,2′ bpy) 2] (C) (H 2oba=4,4′ oxybis(benzoic acid), 2,2′ bpy = 2,2′ bipyridine) were hydrothermally synthesized by altering the metal/carboxylate ratios or in the presence of an additional chelate 2,2′ bpy ligand, and characterized by single crystal X ray diffraction. The results show that different metal/carboxylate ratios can influence the polymeric structures and the presence of 2,2′ bpy ligand alters the topology of the framework from two dimensional to three dimensional.

Synthesis, Crystal Structure and Luminescence of a New Europium(Ⅲ) Coordination Polymer with Imidazole Carboxylic Ligand

A new luminescent compound, {[Eu3（L）4（H2 O）8]·（NO3）·4 H2 O}n（1, H2 L = 2-（pyridine-3-yl）-imidazole-4,5-dicarboxylic acid） has been solvothermally synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction. 1 crystallizes in monoclinic, space group C2/c with a = 21.0183（19）, b = 9.5227（6）, c = 28.227（3） ?, β = 106.885（5）o, V = 5406.1（8） ?3, Dc = 2.038 g/cm3, μ = 3.358 mm-1, Mr = 1658.76, F（000） = 3247, Z = 4, the final R = 0.0488, wR = 0.1195 and S = 1.075. The deprotonated L ligand employs a μ4-bridge to coordinate with three Eu（Ⅲ） ion, forming a wave-like（3,4）-connected 2 D structure. The existence of π···π interaction between the pyridine rings of L ligands leads to an infinite 3 D network. Furthermore, the thermal analysis, powder diffraction and solid-state photoluminescent properties of compound 1 have also been investigated.

A Y(Ⅲ)-organic Coordination Polymer Constructed from 2-(Pyridine-4-yl)-1H-imidazole-4,5-dicarboxylate and Oxalate Ligands: Structure and Luminescent Property

A novel compound, {[Y（HPIDC）（OX）1/2（H2O）]·2H2O}n （1, H3PIDC = 2-（pyridin-4- yl）-1H-imidazole-4,5-dicarboxylic acid, H2OX = oxalic acid）, has been synthesized under hydrothermal conditions and characterized by thermal analysis （TGA）, powder X-ray diffraction （PXRD）, and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic space group P21/c with a = 8.342（8）, b = 14.61（1）, c = 11.487（1）, β = 90.78（9）°, V = 1400.4（2）3, Z = 4, C11H11N3O9Y, Mr = 418.14, Dc = 1.983 g/cm3, F（000） = 836, Rint = 0.0509, T = 293（2） K, μ = 4.240 mm-1, the final R = 0.0477 and wR = 0.1125 for 2770 observed reflections with I 2σ（I）. Compound 1 exhibits a 3D framework and generates the 1D open channels filled with free water molecules. The structure of 1 can be rationalized as a diamondoid network when the atom yttrium is regarded as a 4-connected node linking four surrounding yttrium atoms. The luminescent property of compound 1 is also investigated.

Syntheses and Crystal Structure of Erbium(Ⅲ) Coordination Polymers with Two Flexible Double Betaine Ligands

Two new polymeric erbium(Ⅲ) complexes of two flexible double betaine ligands have been synthesized and characterized by X-ray analysis. In {[Er(L1)(H2O)4)Cl3 H2O}n (1) (L1 = 4, 4’ -trimethylenedipyridinio-N, N’-diacetate ), the erbium(Ⅲ) ions form a two-dimensional metal carboxylate layer in which each pair of Er(Ⅲ) atoms is bridged by two syn-anti μ-carboxylato-o,o’ groups, Adjacent layers arecross-linked through hydrogen bonds among aqua ligands, lattice water molecules andchloride ions to form a three-dimensional network. Complex l, C17 H28 N2 O9 ErC13 (Mr =676.0) is monoclinic, space group C2, with a= 27. 408(4), b= 9. 645 (3), c= 9. 423(2) A, p=1loo. 85(1)’, V=2446. 2(9) A’, Z=4, D=l. 836 g/cm’, F(OOO) =1332, μ(MoKa) = 38.06 cm-1, R=0. 048 for 2451 reflections with I>2σ(I). { [Er(L2 ) (H2O)4]Cl3. 5H2O}. (2) (L2=1, 3-bis (pyridinio-4-carboxylato) propane) comprises lanthanide carboxylate chains built from centrosymmetric dimeric units crosslinked by a pair of L2 ligands, discrete anions and lattice water molecules. In the dimeric unit of complex 2, each pair of metal ions is bridged by four syn-syn μ-carboxylatoO, O’ groups that are oriented nearly perpendicular to each other about the metal-metalaxis. The metal carboxylate chains of complex 2 are further cross-linked by hydrogenbonds to form a three-dimensional network. Complex 2, C15 H32 N2O13 ErCl3 (Mr=722.0) belongs to the monoclinic space group C2/m with a=16. 564 (3), b=15. 839(3), c=11. 792(4) , β=122. 27(1)°, V=2616(1), Z=4, Dc=1.833 g/cm3,F(000) =1436, μ (MoKa) = 35. 75 cm-1, R =0.043 for 2436 observed reflectionswithI>2σ(I).

Synthesis and Crystal Structure of a 2D Coordination Polymer:[Nd_2(PDB)_2(CH_3COO)_2(H_2O)_3]

A novel coordination polymer [Nd2（PDB）2（CH3COO）2（H2O）3] （H2PDB = pyridine3,4-dicarboxylic acid） has been synthesized by the reaction of Nd（CH3COO）3 with pyridine3,4-dicarboxylic acid under hydrothermal conditions. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the composition and crystal structure of the title complex which belongs to the triclinic system, space group P^-1 with a = 6.9409（14）, b = 7.5497（15）, c = 22.530（5）A, α = 84.79（3）, β = 88.15（3）, γ= 75.55（3）^o, C18H18N2O15Nd2, Mr = 790.82, Z = 2, V = 1138.5（4） A^3, Dc = 2.307 g/cm^3,μ = 4.593 mm^-1, -6≤h≤8, -5≤k ≤8, -26≤l≤ 26, F（000） = 760, Rint = 0.0298, R= 0.0314 and wR= 0.0695 （I〉 2σ（I））. Nd（1） and Nd（2） are linked into zigzag chains by carboxylate groups of acetate with interesting μ3-η^2：η^2 fashion. The zigzag chains are bridged by PDB to form a 2D framework, and a 3D supramolecular network is further constructed via π-π stacking.

铟基配合物材料的刚果红吸附性能及其机理研究

含有机染料的废水会导致严重环境污染,有效去除废水中有机染料污染物的研究广受关注。本研究利用均苯四甲酸和四水合硝酸铟作为原料,通过直接沉淀法和溶剂热法成功组装了两个铟基配合物材料(In-CP#1和In-CP#2),并对其进行了表面形貌、红外光谱、X-射线粉末衍射、比表面积以及热重表征。同时,将两化合物作为吸附剂,系统研究了吸附时间和有机染料初始浓度对其吸附性能的影响及其吸附机理。结果表明,两化合物的吸附机理主要是化学作用,且吸附过程符合准二级动力学特征,但并不符合Langmuir单分子层吸附模型。

Synthesis,structure and near-infrared luminescence of a new 2D praseodymium(Ⅲ) coordination polymer

A novel coordination polymer,[Pr2（BIPA）3（H2O）2].2H2O（1）（H2BIPA=5-bromoisophthalic acid）,was prepared by hydrothermal synthesis and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal was of monoclinic system,space group C2/c,with a=1.98037（14）,b=1.44189（14）,c=2.15281（18） nm,β=95.220（2）°,V=6.1218（9） nm3,C24H17Br3O16Pr2,Mr=1082.93,Dc= 2.350 g/cm3,F（000）=4096,μ=7.136 mm-1 and Z=8.The final R1=0.0608 and wR2=0.1371 for 5624 observed reflections（I2σ（I））.Complex 1 featured an interesting 2D layer containing {Pr2（CO2）3}n right-handed and left-handed helical chains.Furthermore,hydrogen bonds linked the adjacent 2D layers to form a 3D supramolecular framework.Moreover,the near-infrared luminescent properties of 1 were also investigated in the solid state.

Three new Cu(Ⅱ)-Ln(Ⅲ) heterometallic coordination polymers constructed from quinolinic acid and nicotinic acid: Synthesis, structures, and magnetic properties

Three new Cu（Ⅱ）-Ln（Ⅲ） heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu（LI）2（L2）（H2O）2]· mH20},, （Ln = La（1）, Nd（2）, Gd（3）, m = 2 （for 1）, 1 （for 2, 3）, H2L1 = quinolinic acid, HE2 = nico- tinic acid）, have been synthesized and characterized. 1 has a two-dimensional （2D） layer structure with a Schlifli symbol of （44.62）, while complexes 2 and 3 are isostructural and have three-dimensional （3D） structures with a Schlafli symbol of （3.4.5）2（32.42.52.6]4.74.83.9）（32.63.7） of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists be- tween NdIn and Cun in 2, while weak ferromagnetic coupling between GdⅢ and CuⅡ in 3. The difference of magnetic properties between 2 and 3 has been discussed.

镧(Ⅲ)与壳聚糖配位聚合物的形成及其催化作用

本文首次报道了稀土镧离子Ｌａ（Ⅲ）与壳聚糖（ＣＳ）配位聚合物（Ｌａ－ＣＳ）的形成、该配位聚合物的ｘ射线光电子能谱、红外光谱、热分析、紫外光谱和电导率的表征和Ｌａ－ＣＳ配位聚合物在Ｎａ２ＳＯ３的存在下对于甲基丙烯酸甲酯（ＭＭＡ）聚合反应的催化作用。结果表明，配位聚合物中配体ＣＳ的仲羟基氧原子和氨基氮原子均参与与配位，Ｌａ（Ⅲ）与ＣＳ单体单元的配位比是１∶５，即Ｌａ（Ⅲ）的配位数是１０。Ｌａ－ＣＳ配位聚合物－Ｎａ２ＳＯ３体系对ＭＭＡ聚合具有较高的催化活性，聚甲基丙烯酸甲酯（ＰＭＭＡ）收率达７５％以上，ＭＭＡ按自由基机理进行聚合。

系列Ln(Ⅲ)配位聚合物(Ln:Eu,Sm,Tb,Gd)的合成及其荧光分析

采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu2(C9H7O2)6(C9H7O2H)(C2H5OH)]n(1)、[Sm(C9H7O2)3]n(2)、[Tb(C9H7O2)3]n(3)和[Gd(C9H7O2)3]n(4)(C9H8O2=肉桂酸)。通过X射线单晶衍射确定了它们的结构。这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。

Three new Cu(Ⅱ)-Ln(Ⅲ) heterometallic coordination polymers constructed from quinolinic acid and nicotinic acid: Synthesis, structures, and magnetic properties

Three new Cu(II)-Ln(Ⅲ) heterometallic coordination polymers based on two N-heterocyclic carboxylic ligands, {[LnCu(L1)2(L2)(H2O)2]·mH2O}n (Ln = La(1), Nd(2), Gd(3), m = 2 (for 1), 1 (for 2, 3), H2L1 = quinolinic acid, HL2 = nicotinic acid), have been synthesized and characterized. 1 has a two-dimensional (2D) layer structure with a Schl?fli symbol of (44.62), while complexes 2 and 3 are isostructural and have three-dimensional (3D) structures with a Schl?fli symbol of (3.4.5)2(32.42.52.614.74.83.9)(32.63.7) of 3-nodal net. Magnetic investigations suggest that antiferromagnetic coupling exists between NdⅢ and CuII in 2, while weak ferromagnetic coupling between GdⅢ and CuII in 3. The difference of magnetic properties between 2 and 3 has been discussed.

以二羧基苯氧乙酸为配体的一维钆(Ⅲ)配位聚合物的合成及晶体结构

利用Williamson合成法合成了3,5-二甲氧酰基苯氧乙酸甲酯(ML),并以之作为配位前驱物与氯化钆在水热条件下发生原位水解-配合反应,得到了3,5-二羧基苯氧乙酸(H3L)与Gd髥形成的一维配位聚合物[H3L2Gd(H2O)4]n,用X-射线单晶衍射法对其进行了结构表征。测定结果表明,该配合物结晶于单斜晶系,C2/c空间群,晶胞参数:a=1.534 4(3)nm,b=2.074 9(3)nm,c=0.716 08(16)nm,β=103.49°,V=2.216 90(225)nm3,Z=4,Dc=2.117 01 g.cm-3。Gd(III)金属中心处于扭曲的双帽三棱柱配位几何构型的中心,与来自4个配体的4个羧基氧原子结合,4个配位水分子则占据了配位环境中剩余的4个顶点。Gd髥金属中心由二齿的配体以Gd-O键连接成Ln2L4型结构单元,并进一步通过共用Gd髥金属中心的方式连接形成一维长链结构。

钕(Ⅲ)与壳聚糖配位反应的研究

本文将Ｎｄ（ＮＯ３）３与壳聚糖（ＣＳ）作用，制备了Ｎｄ（Ⅲ）与ＣＳ的配位聚合物（Ｎｄ／ＣＳ配位聚合物）。首次对Ｎｄ／ＣＳ配位聚合物的Ｘ射线光电子能谱、红外光谱、Ｘ射线粉末衍射谱、紫外可见光谱和电导率进行讨论和研究。推断Ｎｄ／ＣＳ配位聚合物的组成为每一个Ｎｄ（Ⅲ）与５个ＣＳ链节单元的氨基及部分质子化氨基的Ｎ原子和脱质子的仲羟基Ｏ原子配位，中心Ｎｄ（Ⅲ）的配位数为１０。

基于三核锰(Ⅲ)结构单元的二维配位聚合物的合成、结构和磁性研究(英文)

新合成了钠离子桥联三核锰结构单元的配位聚合物{[NaMnⅢ3O(sao)3(tfbdc)(H2O)4].0.5H2O.2CH3CH2OH}n(1)(H2tfbdc=2,3,5,6-四氟对苯二甲酸;H2sao=水杨醛肟),对其进行了元素分析、红外光谱、热重分析和单晶X-射线衍射结构分析。配合物属于三斜晶系,空间群P1。该配合物是一个由三核锰结构单元[Mn3O]构成的、钠离子和四氟对苯二甲酸桥联的二维配位聚合物。磁学性质研究表明,该配合物中锰离子之间存在着反铁磁性耦合作用。

一个新型氰根桥联铁(Ⅲ)-铜(Ⅱ)大环配位聚合物的合成和晶体结构

合成了新型大环配位聚合物 [Cu(L) ]2 [Fe2 (H2 O) (CN) 10 ]·8H2 O(L =1,8-二正丙基- 1,3,6 ,8,10 ,13-六氮杂 - 14-冠 - 4 ) ,用元素分析、ICP分析、IR光谱对配合物进行了表征 ,X -射线衍射测定了其单晶结构 .结果表明 ,该晶体属正交晶系 ,Pddd空间群 ,a =1.8310 (4)nm ,b =2 .6 0 6 0 (5)nm ,c =3.16 80 (6 )nm ,α =β =γ =90° ,V =15.116 (5)nm3,Z =8,dc=1.0 85g/cm3,F(0 0 0 ) =52 0 0 ,R1=0 .10 2 4 ,WR2 =0 .2 6 57,GOF(F2 ) =0 .992 .该配合物结构中氰根桥联铁 (Ⅲ )和铜 (Ⅱ ) ,形成Fe -CN -Cu -NC -Fe一维链 ,链与链之间经由Fe-O(H2 O) -Fe而相互联结 ,形成相互交叉的网状结构 .铁和铜均形成 6配位畸变 8面体构型 .

以草酸、碳酸根构筑的一个钕(Ⅲ)配位聚合物的晶体结构和荧光性质(英文)

水热条件下采用Nd2(CO3)3和草酸钠作为反应物合成出一个新的三维钕(Ⅲ)配位聚合物{[Nd2(ox)(cb)2(H2O)2]·3H2O}n(1)(ox=草酸,cb=碳酸),并分别用元素分析、红外光谱、差热分析、X-射线粉末衍射和X-射线单晶衍射等表征了该结构。晶体结构分析结果表明:μ2桥联的草酸根离子与μ4桥联的碳酸根离子将钕离子连接成三维微孔结构,沿b轴和c轴方向分别具有孔径大小为0.53 nm×0.41 nm和0.59 nm×0.84 nm的通道。拓扑分析结果表明化合物1为(4,5)连接类型。荧光分析表明常温固态下配合物1发射近红外荧光。

3-羧基苯氧乙酸根及邻菲咯啉构筑的钕(Ⅲ)配位聚合物的合成、晶体结构及磁性质(英文)

在水热反应条件下,采用3-羧基苯氧乙酸(3-H2CPOA=3-carboxyphenoxyacetatic acid)和phen(phen=1,10-phenanthroline)与NdCl3·6H2O反应,合成了1个具有三维结构的配位聚合物[Nd(3-CPOA)1.5(phen)]n(1),并对其结构和磁性质进行了研究。结构分析结果表明该聚合物的晶体属于单斜晶系,P21/c空间群。2个钕(Ⅲ)离子、3个3-CPOA2-配体和2个phen配体形成了1个[Nd2(3-CPOA)3(phen)2]双核轮状结构单元,这些双核单元通过钕(Ⅲ)离子与3-CPOA2-配体的配位作用形成了1个三维框架结构。磁性研究表明,该聚合物中相邻的钕(Ⅲ)离子之间存在很强的反铁磁相互作用。

2种Nd(Ⅲ)配聚物的合成及近红外发光性能研究

采用水热合成方法,以2,5-吡啶二羧酸和间苯二甲酸为主要配体,合成了2种具有3D无限网状结构的Nd(Ⅲ)配聚物:[Nd(2,5-pdc)(OAc)(H2O)·2H2O]n(1)和[Nd(1,3-bdc)(OAc)(H2O)2·H2O]n(2)(OAc-=醋酸根,2,5-pdc2-=2,5-吡啶二羧酸根,1,3-bdc2–=间苯二甲酸根).通过X射线衍射确定了它们的晶体结构,并测定了它们的IR光谱、UV-Vis-NIR光谱及近红外发射光谱,并对各光谱进行了分析指认.重点研究了它们的近红外发光性能,这2种配聚物的NIR发射光谱都呈现出Nd(Ⅲ)离子的特征发光,并且与理论发射带相比,出现蓝移现象,这可以从它们的UV-Vis-NIR吸收光谱得到佐证.通过对比这2种配聚物的发光性能,研究了不同配体对Nd(Ⅲ)离子特征发光的敏化作用.

两种Ln(Ⅲ)配聚物的合成、结构及光物理研究

采用水热合成方法得到了2种Ln(Ⅲ)配聚物[Ln(C8H7O3)3]n(Ln=Er(1)和Yb(2)).X-射线单晶结构分析表明,2个配聚物是同构的,均由对甲氧基苯甲酸根为桥形成的1D链状结构.Ln(Ⅲ)离子为8配位,8个氧原子均来自对甲氧基苯甲酸根.配体对甲氧基苯甲酸根采取桥双齿和桥三齿2种模式桥连Ln(Ⅲ)离子.通过红外光谱(IR)、电子吸收光谱(UV-Vis-NIR)及荧光光谱(FP)对配聚物进行了表征及光物理性质研究.研究表明,2种配聚物在可见区的荧光发射相对较弱.