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.

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.

In-Situ Composition and Luminescence of Europium and Terbium Coordination Polymers/PEMA Hybrid Thick Films

Europium and terbium coordination polymers of pyridine-3-carboxylic acid were in-situ composed with ethyt methacrylate （ EMA ）. With the polymerization of EMA monomer and the formation of europium and terbium coordination polymers of pyridiae- 3-carboxylic acid, the transparent hybrid thick fihns composed of [ Eu（ NIC ）3 ]n （ [ Tb（ NIC）3 ]n ） and poly ethyl mettuwrylate （ PEMA ） have been prepared. The luminescence properties and energy transfer of these polymeric composites were studied with absorption spectra, fluorescent excitation trod emission spectra in detail. All the hybrid thick films composed of terbium coordination polymer show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable sabstrate for the luminescence of terbium ions. In the range of camposing concentration of luminescent species （0.01,0.025,0.05,0.1 mmol /15 mL EMA ）, emission intensities increase with the increasing of corresponding composing concentration and the concentration quenching effect does not take place.

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.

One Novel Red-luminescent Coordination Polymer of Eu-p-ben- zenedicarboxylate with Nitrogen-donor-containing Lewis Base

The crystal structure of novel coordination polymer with excellent characteristic luminescence of Eu3+, the three-dimentional network of {Eu2(p-BDC)3(Phen)2(H2O)2}n is presented.

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.

One-dimensional (1D) europium coordination polymer wires:Synthesis,characterization and photoluminescence properties

1D europium coordination polymer wires were successfully prepared by reacting europium chloride with tributyl phosphate(TBP) at 160 oC for 12 h. The products were characterized by XRD,IR,TG,DTA,SEM,and EDS. SEM results showed that the wires were with diameters ranging from several hundreds of nanometers to ～5 μm and lengths going up to several hundreds of micrometers. Influencing factors such as the dosage of reactants and reaction time on the preparation were systematically investigated. Strong emission centering at 590 nm was realized in the coordination polymer wires on excitation at 395 nm.

Synthesis and Properties of a Novel 3D Europium Coordination Polymer with Helical Chain and （3,6）-Connected rtl Net

The first coordination polymer of 2,2＇-（（4-carboxymethyl-1,3-phenylene）bis（oxy）） diacetic acid （H3L） with eu- ropium（[II） ion, [Eu（L）（H2O）]＇3H2O （1）, has been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a 3D coordination polymer with helical chain and rtl topology of the point symbol （4·6^2）2（4^2·6^10·8^3） based on [Eu2（COO）4] as secondary building unit （SBU）. Furthermore, the luminescent and magnetic properties of complex 1 are studied.

含稀土铕(Ⅲ)配位聚合物的研究 Ⅰ.铕(Ⅲ)-噻吩甲酰三氟丙酮-聚(苯乙烯-丙烯酸)的结构表征

研究了铕 (Ⅲ )和噻吩甲酰三氟丙酮 (HTTA)形成的有机配合物与聚 (苯乙烯 丙烯酸 )PSAA在不同pH值时发生配位反应得到配位聚合物NaEu(Ⅲ ) TTA PSAA的 3种样品 (a) ,(b) ,(c)。红外光谱、紫外光谱、X光电子能谱的测试表明了Eu3+ 分别与PSAA ,TTA- 发生配位。元素分析和电导率测定结果证明了配位组成和结构在不同的 pH条件下发生变化。结果表明 ,配合物试样 (a) ,(b) ,(c)中Eu3+ 的含量分别为11 89% ,12 5 5 % ,13 4 1%。

铕(Ⅲ)-二苯甲酰甲烷-聚丙烯酸/聚(苯乙烯-丙烯酸)配合物及其性质研究

研究了铕(Ⅲ)和二苯甲酰甲烷(HDBM)形成的有机配体NaEu(DBM)4与聚丙烯酸(PPA)(Mr=5000)、聚(苯乙烯-丙烯酸)(PSAA)(Mr=3000)发生配位反应分别得到配合物Eu(Ⅲ)-DBM-PAA和NaEu(Ⅲ)-DBM-PSAA,得率分别为89.7％和87.3％。红外光谱、紫外光谱、X光电子能谱的测试表明了Eu3+分别与PAA,PSAA和DBM-发生配位。元素分析和电导率测定结果证明了一个Eu3+分别与PAA中二个链节或PSAA中三个链节的羧基和一个DBM-发生配位。Eu3+离子在配合物Eu(Ⅲ)-DBM-PAA和NaEu(Ⅲ)-DBM-PSAA中的质量分数分别为28.46％和12.23％。荧光光谱表明,常温下配合物在紫外光下发出强的红光,主要是Eu3+离子的5D0→7F2的能级跃迁。

聚丙烯酸/聚(苯乙烯-丙烯酸)二苯酰基甲烷铕(Ⅲ)配合物的合成及其荧光性能

铕 ( )和二苯甲酰甲烷 (HDBM)形成的有机配合物与聚丙烯酸 (PAA) (Mn=5 0 0 0 )、聚 (苯乙烯 -丙烯酸 ) (PSAA) (Mn=3 0 0 0 )发生配位反应 ,分别得到配位聚合物 Eu( ) -DBM-PAA和 Na Eu( ) -DBM-PSAA,产率分别为 89.7%和 87.3 % .红外光谱、紫外光谱、X光电子能谱测试表明 ,Eu3+分别与 PAA,PSAA和 DBM-发生配位 ,元素分析和电导率测定结果证明 ,1个 Eu3+分别与 PAA中 2个链节或 PSAA中3个链节的羧基和 1个 DBM-发生配位 .Eu3+离子在配位聚合物 Eu( ) -DBM-PAA和 Eu( ) -DBM-PSAA中的含量分别为 2 8.4 6%和 1 2 .2 3 % .荧光光谱表明 ,常温下配位聚合物在紫外光下发出强的红光 ,主要是Eu3+离子的 5D0 → 7F2

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.

含稀土铕(Ⅲ)配位聚合物的研究——铕(Ⅲ)噻吩甲酰三氟丙酮苯乙烯丙烯酸共聚物的研究

研究了铕 (Ⅲ )和噻吩甲酰三氟丙酮 (HTTA)形成的有机配合物与苯乙烯 丙烯酸共聚物 (PSAA)在不同pH值时发生配位反应得到配位聚合物NaEu(Ⅲ ) TTA PSAA的 3种样品 (a)、(b)、(c) .红外光谱、紫外光谱、X光电子能谱、DTA TG等测试手段证实Eu3+ 分别与PSAA、TTA- 发生配位 .元素分析和电导率测定结果证明了配位组成和结构在不同的pH条件下发生变化 .结果表明 ,配合物试样 (a)、(b)、(c)中Eu3+ 的含量分别为11 89%、12 5 5 %和 13 4 1% .由于配合物中存在着Eu3+ 分别与TTA- 和PSAA分子中羧基的配位作用并进一步交联 ,因此配合物样品均不溶于大部分有机溶剂 ,只能溶于N ,N 二甲基甲酰胺和丙三醇和异丙醇的混合溶剂 ,而且耐热性能均提高 .该配合物均是褐色固体 .荧光光谱表明 ,样品在常温、紫外光下发出强的红光 ,主要是Eu离子的5D0 →7F2 的跃迁 .讨论了溶剂、pH值对配合物荧光强度的影响 .当pH =10时 ,合成的配合物有最好的荧光性质 .

含稀土铕(Ⅲ)配位聚合物的研究

将铕的有机配合物NaEu(TTA)4与聚(苯乙烯 丙烯酸)(PSAA)反应制备了铕配位聚合物[Eu(Ⅲ) TTA PSAA],用电导、DTA TGA、荧光光谱等对其进行了表征。由于配合物中存在着Eu3+分别与TTA-和PSAA分子中羧基的配位作用,并进一步交联,因此配合物样品均不溶于大部分有机溶剂,只能溶于N,N 二甲基甲酰胺和丙三醇/异丙醇的混合溶剂,且耐热性得到提高。配合物为褐色固体,在常温、紫外光下发出红光,主要是由于Eu3+离子的5D0→7F2跃迁。讨论了pH值对配合物荧光强度的影响,当pH=10时,合成的配合物具有最好的荧光性。

两种吡啶多羧酸与稀土Eu(Ⅲ)配合物的结构与光致发光性质

用高氯酸铕和3,5-吡啶二甲酸、2,4,6-吡啶三甲酸在水热条件下反应合成了一个含有两种吡啶多羧酸阴离子配体的三维配位聚合物{[Eu2(2,4,6-Hptc)(3,5-pdc)2(H2O)8]·6H2O}n(1)(2,4,6-H3ptc=2,4,6-吡啶三甲酸;3,5-H2pdc=3,5-吡啶二甲酸)。单晶X-射线衍射分析表明,该配合物属单斜晶系,C2/c空间群,晶胞参数为a=2.0106(11)nm,b=1.1048(6)nm,c=1.7591(10)nm,β=112.117(8)°,α=γ=90°。配合物的中心Eu^(3+)与九个氧原子配位,其中五个氧原子来自配体羧基氧原子,四个来自配位水分子,这些氧原子形成了变形三帽三棱柱结构。3,5-pdc阴离子的两个羧酸根分别以螯合方式连接两个Eu^(3+),形成一维链状结构。2,4,6-Hptc以铵盐形式用2-和6-位羧基配位,4-位羧基没有与金属离子配位,通过2,4,6-Hptc的配位将由3,5-pdc与Eu^(3+)形成的一维链连接成一维梯状链结构。该配合物在紫外光的激发下显示红色荧光,具有良好的光致发光性质。

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。