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).

Syntheses and Crystal Structures of Two New Ag(Ⅰ) Complexes with Betaine Derivative: Structure Changes via Metal-to-ligand Ratio

Two new Ag（I） complexes {Ag2（L）（NO3）（H2O）}n（1） and {Ag（L）}n·nH2O（2） have been synthesized via the reaction of silver nitrate and betaine derivative 1-carboxymethylpyridinium-3-carboxylate（L） by only changing the metal-to-ligand ratio. The results of X-ray crystallographic analysis indicate that complexes 1 and 2 both crystallize in the monoclinic space group P21/c with a = 5.0809（14）, b = 17.390（5）, c = 13.399（4）, β = 91.677（5）o, V = 1183.4（6）3, Z = 4, Mr = 475.90, Dc = 2.671 g/cm3, F（000） = 912, μ = 3.352 mm-1, S = 1.259, the final R = 0.0320 and wR = 0.0831 for 2036 observed reflections with I 〉 2σ（I） for 1 and a = 12.180（2）, b = 5.0283（10）, c = 14.396（3）, β = 94.87（3）o, V = 878.5（3）3, Z = 4, Mr = 306.02, Dc = 2.314 g/cm3, F（000） = 600, μ = 2.294 mm-1, S = 1.053, the final R = 0.0283 and wR = 0.0684 for 2011 observed reflections with I 〉 2σ（I） for 2. Complexes 1 and 2 both feature a unique 2D structure. For 1, the 2D undulated network consists of 1D infinite helical chains running parallel to the b axis, while for 2, the 2D network is made up of 1D tubes along the b axis. Moreover, the Ag…Ag interactions in complexes 1 and 2 are also discussed.

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescence of a Novel Two-dimensional Cd(Ⅱ) Coordination Polymer

A new coordination polymer, [Cd2（bptc）（L）2（H2O）2]·5H2O（1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline and H4 bptc = 3,3＇,4,4＇-biphenyltetracarboxylic acid）, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 18.868（4）, b = 7.2111（14）, c = 19.464（4）A, β = 95.75（3）°, C54H31Cd2Cl2F2N8O15, Mr = 1365.57, V = 2635.0（9）A3, Z = 2, Dc = 1.721 g/cm^3, S = 1.034, μ（MoKα） = 0.995 mm^–1, F（000） = 1358, R = 0.0501 and wR = 0.1076. In 1, each bptc anion bridges four Cd（II） atoms to form 2D layer structures, which are further extended by π-π stacking interactions into a 3D supramolecular architecture. The thermal behavior and luminescent properties of the compound have also been studied.

Syntheses, Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

Five new coordination polymers Cu（phen）（H2O）（phth）·CH3OH（1）, [Cu（2,2′-bipy）（H2O）]（phth）·3.5H2O（2）, Zn（phen）（phth）（H2O）·1.125H2O（3） and [M（4,4′-bipy）（H2O）2]（phth）·2H2O[M=Zn（4）, Mn（5）]（H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline） have been synthesized from the amino acid derivatives（phthalyl-l- valine, H2L） and structurally characterized. H2L was hydrolyzed into phth2- group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3''-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L（o-bdc）]n（1） and [Zn L（mbdc）]_n·n H_2O（2）（L = 4？-（3-pyridyl）-3,2？：6？,3？？-terpyridine,H_2（o-bdc） = benzene-1,2-dicarboxylic acid,H_2（m-bdc） = benzene-1,3-dicarboxylic acid）,were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016（2）,b = 11.3815（11）,c = 19.8071（17） ？,β = 133.961（2）°,V = 4546.2（7） ？3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F（000） = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ（I） and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003（14）,b = 11.9152（11）,c = 26.633（3） ？,β = 94.320（2）°,V = 4936.5（8） ？~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^（-1）,F（000） = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ（I） and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.

Solvothermal Synthesis, Crystal Structure and Luminescence Property of a 1D Silver(Ⅰ) Coordination Polymer

An unprecedented one-dimensional coordination polymer [Ag2(PhP O3 H)2(DPPP)]n(1) based on phenylphosphonic acid(Ph PO3 H2) and 1,3-bis(diphenyphosphino)propane(DPPP) has been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal-X-ray diffraction analyses revealed that the complex crystallizes in triclinic system, space group P(16). The coordination geometry of each Ag(I) ion is planar trigonal. Two kinds of rings were found in 1, such as the four-membered ring with Ag2 O2 and the eight-membered ring with Ag2 O4 P2 constructed by PhP O3 H- ligands, which were then connected by DPPP ligands forming a zigzag type chain. Moreover, the light absorption and luminescent property of 1 were also investigated.

Effect of Substituent Groups on the Syntheses of Two Ag Coordination Polymers Based on Tetrazole-yl Acylamide

Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag（NTAA） （1, H-NTAA = N-（1H-tetrazol-5-yl）acetamide） and Ag（NTPA） （2, H-NTPA = N-（1H-tetrazol- 5-yl）propionamide） have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 features a 3-connected 4.82-fes network and compound 2 displays a ladder-like chain. The different structures between 1 and 2 are mainly related with the substituent groups oftetrazole-yl acylamide.

A Novel Coordination Polymer, [Ag_4~I (bpdc)(H_2bpdc)(Hbpdc)_2]_n (bpdc=2,2'-bipyridyl-3,3'-dicarboxylate): Coordination Models of bpdc Ligands

A novel coordination polymer, [Ag4(bpdc)(H2bpdc)(Hbpdc)2]n (bpdc=2,2'-bipyridyl-3,3'-dicarboxylate), was hydrothermally synthesized at 403 K and structurally characterized by single crystal X-ray diffraction analysis. The compound crystalizes in the monoclinic space group C2/c with a=1.9516(4) nm, b=1.9503(4) nm, c=1.2566(3) nm, and β=112.48(3)°. In the two-dimensional crystal structure, AgI center is coordinated, in a scarce coordination environment, double-capped tetrahedron, by one bpdc ligand to form N—Ag—N chelate bond via two pyridyl N atoms, and other two bpdc ligands to form two O—Ag—O chelate bonds, respectively, via two carboxyl O atoms. The bpdc ligands are present in one non-protonated form, bpdc, and two protonated forms, Hbpdc and H2bpdc, which all act as μ3-ligand in a hexadentate fashion (N, N'; O, O'; O, O') to coordinate with three Ag centers, respec- tively, through the three chelate bonds. This coordinated fashion of bpdc ligand is first found in the title compound. UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 3.1 eV.

Assembly of Ag(I) Polymers with Thioether-S Binding and Homochiral Helices

A novel coordination polymer [Ag(pyta)]n (pyta? = 4-pyridylthioacetate) containing b ound thioether sulfurs and single-stranded helical chains has been synthesized and structurally characterized.

New Type of Polymeric Chain Constructed by Exo-bidentate Binaphthol Derivative

The self-assembly of a racemic exo-bidentate ligand 2,2＇-bis（4-pyridylmethyloxy）-1,1＇-binaphthyl, namely Rac-L, with cadmium（Ⅱ） salt gave rise to a new one-dimensional polymer, which has been characterized by single crystal X-ray diffraction analysis. The polymer crystallizes in a triclinic space group P-1 with unit cell parameters： a=0.6976（1） nm, b= 1.30160（14） nm, c= 1.71146（17） nrn.α= 105.141（3）°, β=94.263（5）°, γ= 100.405（4）°, V= 1.4633（2） nm^3, Z=2, C32H29CdCl2N2O4.5, M=696.88, Dc= 1.584 g/cm^3, F（000）=708,μ（Mo Kα）=0.972 mm^-1. The final R and wR are 0.0498 and 0.1282 for 5079 observed reflections with I≥2σ（I）.

三维银配位聚合物[Ag_3(IN)_2(CF_3COO)]的水热合成与晶体结构

A three-dimensional silver coordination polymer,[(Ag3（IN）2(CF3COO))]（IN=Isonicotinic acid）,was synthesized under mild hydrothermal conditions and characterized by single crystal X-ray diffraction.The compound crystallizes in the triclinic space group P-1,with unit cell parameters a=0.918 48（5） nm,b=1.013 92（6） nm,c=1.067 05（6） nm,Z=2,R1=0.036 5,wR2=0.095 5.The Ag centers are bridged by the IN and CF3CO2 ligands to form three-dimensional structure.There are strong Ag-Ag bond interaction in the framework.

含咪唑基配体的Co(Ⅱ)超分子配合物的合成、晶体结构和光谱性质

采用改进的固相Wittig反应,合成了一种新型的具有电子给受体和π共轭结构的咪唑衍生物1-{反式4-[4-(N,N-二乙基氨基)苯乙烯基]苯}咪唑(C21H23N3,简作L).室温下,将L与Co(SCN)2在甲醇中反应,合成了配合物Co(SCN)2(C21H23N3)4.X射线单晶衍射分析结果表明,该晶体属于三斜晶系,P1空间群,晶胞参数a=0.9317(3)nm,b=1.2753(4)nm,c=1.6691(5)nm,α=89.521(5)°,β=84.591(5)°,γ=80.052(5)°,V=1.9446(11)nm3,Z=1,μ=0.329mm-1,Dc=1.234Mg/m3,F(000)=765,R1=0.0601,wR=0.1381,GOF=1.030,中心原子Co(Ⅱ)的配位数为6,分别与来自4个L的咪唑N及2个SCN-的N配位,形成八面体的空间构型.配合物分子通过非典型氢键和π-π堆积作用形成三维超分子结构.研究结果表明,配合物具有很好的光学性质.

邻菲咯啉衍生物及苯四甲酸构筑的一维铁(Ⅱ)配位聚合物的合成及结构(英文)

水热法合成了1个一维配位聚合物[Fe2L2(btc)(H2O)2]n(L为邻菲咯啉衍生物(2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline,btc为苯四甲酸根),并对该化合物进行了元素分析、红外,热重和单晶X-射线表征。该化合物属于三斜晶系,空间群P1,晶胞参数a=0.756 11(5)nm,b=1.003 63(4)nm,c=1.482 79(9)nm,α=91.190(1)°,β=100.569(2)°,γ=106.966(1)°,V=1.054 68(10)nm3,Z=2,R=0.035 0,wR=0.094 5。在该化合物中,苯四甲酸连接着Fe(Ⅱ)原子形成一维链状结构,链与链之间又进一步地通过π-π相互作用形成二维层状超分子结构,氢键进一步地稳定了此层状结构。

以邻菲咯啉衍生物及1,3-间苯二甲酸为配体的一维链状Cd(Ⅱ)配位聚合物的合成及结构(英文)

在水热条件下,我们利用邻菲咯啉衍生物配体(L=2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)和1,3-间苯二甲酸(1,3-H2BDC)反应得到了一维配位聚合物[Cd2(L)2(1,3-BDC)2]n,并对该化合物进行了元素分析、红外和单晶X-射线表征。该化合物属于三斜晶系,空间群Pī,晶胞参数a=1.080 8(4)nm,b=1.149 5(4)nm,c=1.924 8(7)nm,α=106.482(5)°,β=99.436(6)°,γ=93.093(6)°,V=2 249.2(14)nm3,Z=4,C27H15CdFN4O4,Mr=590.83,Dc=1.745 g.cm-3,F(000)=1 176,μ(Mo Kα)=1.024 mm-1,R=0.044 5和wR=0.111 7。该化合物为一维链状结构,链与链之间又进一步地通过CH-π相互作用形成二维层状超分子结构。

邻菲啰啉衍生物配体和柔性二羧酸共同构筑的钴(Ⅱ)配位聚合物(英文)

通过水热方法合成了一个新的化合物[Co2(L)2(1,5-PDC)2].0.5H2O(L为邻菲啰啉衍生物2-(2-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline,1,5-PDC为庚二羧酸阴离子),并对该化合物进行了元素分析、红外和X射线单晶衍射表征。该化合物属于三斜晶系,空间群P1,晶胞参数C104H86Co4F4N16O17,a=1.108 2(5)nm,b=1.390 2(4)nm,c=1.601 7(6)nm,α=90.806(5)°,β=93.429(3)°,γ=111.312(5)°,V=2.293 0(15)nm3,Z=1,R=0.059 7,wR=0.160 8。在该化合物中,1,5-PDC阴离子桥联着相邻的钴离子从而形成了一维链状结构。存在于相邻链之间的π-π相互作用使一维链形成了二维超分子结构。此外,N-H…O和O-H…N氢键进一步地稳定了此二维超分子结构。

吡嗪席夫碱银配位聚合物的晶体结构、发光性质和抗菌活性

利用2-乙酰基吡嗪和异烟肼在无水乙醇中反应得到席夫碱化合物N-[(1-吡嗪基)-1-亚甲基]异烟酰肼(L)。以L和硝酸银为原料,通过扩散法合成了配位聚合物{[Ag_(3)L_(2)(NO_(3))_(2)]CH_(3)CN}_(n),并通过X-射线单晶衍射、元素分析、红外光谱、荧光光谱对其进行结构解析和性质表征。单晶衍射分析结果表明,该配位聚合物属单斜晶系,P2_(1)/c空间群,晶胞参数为a=0.61170(10)nm,b=1.34708(3)nm,c=2.01869(4)nm,V=1.66106(6)nm^(3),Z=2,Mr=970.19,Dc=1.940 g/cm^(3),配体分子以银离子为连接点形成二维网状结构。荧光光谱分析表明配体和配位聚合物均有较好的发光性能,且配位聚合物荧光强度优于配体。抗菌活性表明,配位聚合物对白色葡萄球菌、藤黄八叠球菌及枯草芽孢杆菌有较好的特异性,具有良好的医药应用前景。

基于萘二甲酸及邻菲咯啉衍生物的铅配位聚合物的合成及结构(英文)

利用水热合成法得到了二维配位聚合物[Pb2(L)(1,4-NDC)2].0.5H2O(1),并对该化合物进行了元素分析、红外、热重和单晶X-射线表征,其中L为邻菲咯啉衍生物配体(1-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)naphthalen-2-ol),1,4-NDC为1,4-萘二甲酸根。该化合物属于三斜晶系,空间群P1,晶胞参数a=0.95078(6)nm,b=1.26511(8)nm,c=1.78591(12)nm,α=78.441(2)°,β=78.620(1)°,γ=77.124(1)°,V=2.025 3(2)nm3。该化合物为二维层状结构,层与层之间又进一步地通过π-π相互作用形成二维双层超分子结构。

一个新颖的二维锌配位聚合物[Zn(L)(1,4-BDC)]_n的合成、结构和表征(英文)

The title coordination polymer,[Zn (L) (1,4-BDC)]n (1) (L =2-(4-fluorophenyl)-1H-imidazo [4,5-f] [1,10] phenanthroline and 1,4-H2BDC=1,4-benzenedicarboxylic acid) has been synthesized by hydrothermal method and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1 with a=0.970 85(16) nm,b=1.076 98(18) nm,c=1.203 6(2) nm,α=63.894(2)°,β=69.051(2)°,γ=80.427(2)°,V= 1.055 4(3) nm3,Z=2,C27H15FN4O4Zn,Mr=543.80,Dc=1.711 g·cm-3,F(000)=552,μ(Mo Kα)=1.220 mm-1,R=0.037 2 and wR=0.084 4. The 1,4-BDC ligands linked the Zn(Ⅱ) atoms to form a two-dimensional layer structure. The π-π stacking interactions between L ligands extended the adjacent layers into a three-dimensional supramolecular network. Finally,the N-H…O hydrogen bonds further stabilizes the structure of 1.

阴离子调控的含反式-双(苯甲酰丙酮)-1,4-环己二胺银配位聚合物的合成、晶体结构及其荧光性质

将配体反式-双(苯甲酰丙酮)-1,4-环己二胺(L)与Ag X(X=NO3-,BF4-,Sb F6-,Cl O4-)进行反应得到4个配合物{[Ag(L)]NO3}n(1),{[Ag(L)(H2O)]BF4}n(2),{[Ag2(L)3](Sb F6)2}n(3),{[Ag(L)]Cl O4}n(4),并用元素分析,红外和X-射线单晶衍射表征了4个配合物的结构。在固体状态下,配合物1和2都形成2D网状结构的配位聚合物,都有2个不同配位类型的配体,不同的是,配合物1中桥连配体的1,4-环己二胺1,4位的C-N键在直立键上,而配合物2中桥连配体的1,4-环己二胺中1,4位的C-N键在平伏键上;配合物3也有2种不同配位类型的配体,但是与配合物1和2不同,配合物3形成1D配位聚合物;配合物4中的配体只有一种配位类型,配合物4形成2D网状结构。4个配合物中,配合物2,3的阴离子未参与Ag(Ⅰ)配位,配合物1和4的阴离子与Ag(Ⅰ)配位。同时,研究了配体和配合物在室温下的固态荧光性质。

邻菲啰啉衍生物与柔性二羧酸构筑的铅(Ⅱ)配位聚合物:合成、结构与表征(英文)

通过水热合成的方法得到了一个新的化合物[Pb2(L1)2(L2)2],并对该化合物进行了元素分析、红外、热重和单晶X-射线表征(H2L1为丁二羧酸阴离子,L2为邻菲啰啉衍生物)。该化合物属于单斜晶系,空间群P21/c,晶胞参数:a=0.795 40(10)nm,b=2.649 0(3)nm,c=1.996 9(2)nm,β=99.784(2)°,V=4.1463(9)nm3,Z=4,R=0.038 0,wR=0.084 5。在该化合物中,丁二酸阴离子连接着铅原子形成一维链状结构。此外,链与链之间的π-π相互作用使一维链形成了三维超分子结构。最后,N-H…29…29O氢键进一步地稳定了此三维超分子结构。