Crystal structures and luminescence of two cadmium(II) polymers constructed from aromatic polycarboxylate and bis(1,2,4-triazol-1-yl)methane ligands

Two new coordination compounds, {[Cd₂(btrm)(ip)₂(H₂O)₂]?·?2H₂O} _n (1) and {[Cd₂(btrm)(hip)₂(H₂O)₄]?·?3H₂O} _n (2) (btrm?=?bis(1,2,4-triazol-1-yl)methane, H₂ip?=?isophthalic acid, H₂hip?=?5-hydroxy isophthalic acid), have been synthesized and structurally characterized. Compound 1 is a 3-D network with CdSO₄ topology. Compound 2 contains 1-D ladder structures, which are interconnected by classical hydrogen-bonding interactions (O–H?···?O) to lead to 3-D supramolecular architectures. Luminescence was performed on 1 and 2, both of which showed strong fluorescent emissions in the solid state at room temperature.     

Preparation,crystal structure and luminescence of lanthanide coordination polymers with 2,2′-dimethyl-4,4′-bipyridine-N,N′-dioxide

Four coordination polymers of the bidentate ligand 2,2′-dimethyl-4,4′-bipyridine-N,N′-dioxide (L), [La(L)(NO₃)₃(H₂O)] _n (1), {[Gd₂(L)₃(NO₃)₆]·6H₂O} _n (2), {[Sm(L)₂(H₂O)₄]·3ClO₄·2L·4H₂O} _n (3) and {[Nd(L)₂(H₂O)₄]·3ClO₄·2L·4H₂O} _n (4) have been synthesized by the diffusing solvent mixture method. Results of X-ray diffraction analysis reveal that 1, with a Ln/L stoichiometry of 1:1, displays a rare 3-D three-fold interpenetrating diamondoid framework, while 2 has a Ln/L stoichiometry of 1:1.5 and exhibits a polycatenane network with a {8²,10} topology and large channels accommodated by water. Complexes 3 and 4, with Ln/L stoichiometry of 1:2, have 3-D two-fold interpenetrating diamondoid structures and large voids. Nonlinear optical property of 2 and luminescence of 3 were also investigated.     

基于半刚性双(噻唑基苯并咪唑)和不同羧酸的五个一维配合物的合成和表征

通过水热或溶剂热合成的方法制备了5个一维配合物{[Zn(btbb)_(0.5)(m-phda)]·0.5H_2O}_n(1),{[Cd_2(btbb)(adtda)_2(H_2O)]·H_2O}_n(2),[Mn_2(btbb)(tbi)_2]_n(3),{[Cd(btbb)_(0.5)(3-Nitro-o-bdc)(H_2O)]·H_2O}_n(4)和[Cd_2(btbb)(tbi)_2]_n(5)(btbb=1,4-双(2-(4-噻唑基)苯并咪唑-1-基甲基)苯,m-H_2phda=间苯二甲酸,H_2adtda=1,3-金刚烷二羧酸,H_2tbi=5-叔丁基间苯二甲酸,3-Nitro-o-H_2bdc=3-硝基-1,2-苯二甲酸)。配合物1是一个包含22元环的一维链。配合物2是一个包含8元环的一维链,并且氮配体在这个一维链中仅仅起到装饰作用。配合物3是一个一维双链结构。配合物4是一个包含14元环的一维链。配合物5是一个阶梯状的一维双链结构。     

四个Cd(Ⅱ)配位聚合物:辅助配体对晶体结构以及荧光性能的影响

采用溶剂热的方法,将配位模式丰富的多羧酸有机配体5-(2-硝基-4-羧基苯氧基)-间苯二甲酸(H3ncpoi)与Cd~(2+)离子以及不同的辅助配体原位组装而成4个新的配位聚合物晶体:[Cd(Hncpoi)(2,2′-bpy)(H2O)]n(1),{[Cd2(Hncpoi)2(bpyp)(H2O)4]·3H2O}n(2),{[Cd2(Hncpoi)2(azpy)(H2O)2]·2H2O}n(3),{[Cd2(Hncpoi)2(dpe)(H2O)2]·2H2O}n(4),其中H3ncpoi为5-(2-硝基-4-羧基苯氧基)-间苯二甲酸,2,2′-bpy为2,2′-联吡啶,bpyp为1,4-二-吡啶基-4-亚甲基-哌嗪,azpy为4,4′-偶氮吡啶,dpe为1,2-二-(4-吡啶基)乙烯。对4个配合物进行了X射线单晶衍射、粉末衍射,元素分析、热重、荧光光谱等表征。X射线单晶结构分析表明,配合物1,2具有一维链状结构,而配合物3,4则具有二维(4,4)格子层状结构,一维链和二维层之间通过分子间作用力连接成三维超分子结构。进一步研究表明,辅助配体的构型、配位方式等对晶体结构具有决定性作用。与此同时,对几个配合物的荧光光谱进行分析,发现不同的辅助配体对配合物的荧光性能有着显著的影响。     

4个Cd(Ⅱ)配位聚合物:辅助配体对晶体结构以及荧光性能的影响

采用溶剂热的方法,将配位模式丰富的多羧酸有机配体5-（2-硝基-4-羧基苯氧基）-间苯二甲酸（H₃ncpoi）与Cd²⁺离子以及不同的辅助配体原位组装而成4个新的配位聚合物晶体：[Cd（Hncpoi）（2,2''-bpy）（H₂O）]_n（1）,{[Cd₂（Hncpoi）₂（bpyp）（H₂O）₄]·3H₂O}_n（2）,{[Cd₂（Hncpoi）₂（azpy）（H₂O）₂]·2H₂O}_n（3）,{[Cd₂（Hncpoi）₂（dpe）（H₂O）₂]·2H₂O}_n（4）,其中H₃ncpoi为5-（2-硝基-4-羧基苯氧基）-间苯二甲酸,2,2''-bpy为2,2''-联吡啶,bpyp为1,4-二-吡啶基-4-亚甲基-哌嗪,azpy为4,4''-偶氮吡啶,dpe为1,2-二-（4-吡啶基）乙烯。对4个配合物进行了X射线单晶衍射、粉末衍射,元素分析、热重、荧光光谱等表征。X射线单晶结构分析表明,配合物1,2具有一维链状结构,而配合物3,4则具有二维（4,4）格子层状结构,一维链和二维层之间通过分子间作用力连接成三维超分子结构。进一步研究表明,辅助配体的构型、配位方式等对晶体结构具有决定性作用。与此同时,对几个配合物的荧光光谱进行分析,发现不同的辅助配体对配合物的荧光性能有着显著的影响。     

Three double- or triple-stranded chains constructed from different cobalt(II) salts and a flexible bis-triazole ligand

Three coordination compounds, {[Co(btrp)₂(H₂O)₂]?·?NO₃?·?H₂O} _n (1), {[Co(btrp)₂(H₂O)₂]?·?H₂O?·?2H₂btc} _n (2), and {[Co(btrp)₃]?·?2ClO₄} _n (3) (btrp?=?1,3-bis(1,2,4-triazol-1-yl)propane; H₃btc?=?benzene-1,3,5-tricarboxylic acid), have been prepared via solvothermal method and characterized by single-crystal X-ray diffraction and elemental analyses. Compound 1 possesses a 1-D double-stranded chain composed of ribbons of 20-membered cycles. Binuclear water clusters link adjacent nitrate anions to form a 1-D supramolecular helix in the structure. Compound 2 has a 1-D double-stranded chain wherein free H₂btc ligands constitute 1-D negative chains through classical hydrogen-bonding interactions (O–H?···?O). Compound 3 exhibits a triple-stranded 1-D chain. For 1–3, 3-D supramolecular structures are consolidated by interchain weak hydrogen-bonding interactions as well as electrostatic interactions.     

Effect of bis-triazole based secondary ligands on the structure of coordination polymers generated from terephthalic acid

Reactions of Zn/Cd(ClO₄)₂·6H₂O and terephthalic acid (H₂BDC) with three bis-triazole ligands afforded three coordination polymers under solvothermal conditions, {[Zn(BDC)(L1)]·H₂BDC}_n (1), {[Zn(BDC)(L2)_0.5]·H₂O}_n (2), and {[Cd₂(BDC)₂(L3)(DMF)(H₂O)₂]·2H₂O]}_n (3) (L1 = bis(4-(4H-1,2,4-triazol-4-yl)phenyl)methane, L2 = bis(4-(4H-1,2,4-triazol-4-yl)phenyl)ethane, and L3 = 1,4-bis(4H-1,2,4-triazol-4-yl)benzene). Solid 1 displayed a 2-D structure which contained two kinds of rings. Both 2 and 3 were 3-D threefold interpenetrating frameworks. Solid 2 showed a α–Po-related net, while 3 exhibited an acs-related network with a binuclear node. Furthermore, the photoluminescent properties of 1–3 were investigated.     

Coordination polymers of CdII and PbII derived from bipyridine–glycoluril: influence of metal‐ion size and counter‐ions

Two new one‐dimensional (1D) coordination polymers (CPs), namely catena‐poly[[[aquacadmium(II)]‐bis(μ‐4b,5,7,7a‐tetrahydro‐4b,7a‐epiminomethanoimino‐6H‐imidazo[4,5‐f][1,10]phenanthroline‐6,13‐dione)] bis(perchlorate) dihydrate], {[Cd(C₁₄H₁₀N₆O₂)₂(H₂O)](ClO₄)₂·2H₂O}_n or {[Cd(BPG)₂(H₂O)](ClO₄)₂·2H₂O}_n, 1 , and catena‐poly[[lead(II)‐bis(μ‐4b,5,7,7a‐tetrahydro‐4b,7a‐epiminomethanoimino‐6H‐imidazo[4,5‐f][1,10]phenanthroline‐6,13‐dione)] bis(perchlorate) dihydrate], {[Pb(C₁₄H₁₀N₆O₂)₂](ClO₄)₂·2H₂O}_n or {[Pb(BPG)₂](ClO₄)₂·2H₂O}_n, 2 , have been synthesized using bipyridine–glycoluril (BPG; systematic name: 4b,5,7,7a‐tetrahydro‐4b,7a‐epiminomethanoimino‐6H‐imidazo[4,5‐f][1,10]phenanthroline‐6,13‐dione), a urea‐fused tecton, in a mixed‐solvent system. The Cd^II ion in 1 is heptacoordinated and the Pb^II ion in 2 is hexacoordinated, with the Cd^II ion adopting a pentagonal bipyramidal geometry and the Pb^II ion adopting a distorted octahedral geometry. Both CPs form infinite linear chain structures which are hydrogen bonded to each other leading to the formation of three‐dimensional supramolecular network structures. Topological analysis of CPs 1 and 2 reveals that the structures exhibit 1D chain‐like arrangements in an AB–AB sequence and shows platonic uniform 2‐connected uninodal topologies. Furthermore, a comparative analysis of a series of structures based on the BPG ligand indicates that the size of the metal ion and the types of counter‐ions used have a great influence on the resulting frameworks and properties.     

Hydrothermal syntheses,and crystal structures of new lanthanide coordination polymers with nitrilotriacetic acid

Hydrothermal reactions of Nd(ClO₄)₃·6H₂O, Gd(ClO₄)₃·6H₂O and Er₂O₃ with H₃NTA (nitrilotriacetic acid) afford three new lanthanide coordination polymers, {[Nd(NTA)(H₂O)]· 2H₂O} _n (1), {[Gd(NTA)(H₂O)]·2H₂O} _n (2) and {[Er(NTA)(H₂O)]·H₂O} _n (3), characterized by elemental analysis and IR spectroscopy. X-ray single crystal structural analyses showed that 1 and 2 are an isomorphous 2D-layered framework containing the nine-coordinated Nd(III) (or Gd(III)), and woven into a 3D suprastructure by interlayer hydrogen bonding while 3 is a 3D structure with eight-coordinate Er(III).     

Cd(II) MOFs based on cadmium/carboxylate units and 4,4′-bis(benzoimidazol-1-yl)bibenzene: syntheses,structures, and luminescence

Solvothermal reactions of CdCl₂·2.5H₂O with 4,4′-bis(benzoimidazol-1-yl)bibenzene (bimbb) and 1,4-benzenedicarboxylic acid (1,4-H₂bdc), 4,4′-biphenyldicarboxylic acid (4,4′-H₂bpdb), 5-methyl-1,3-benzenedicarboxylic acid (5-Me-1,3-H₂bdc), or 1,3,5-benzenetricarboxylic acid (H₃btc) afforded four 3-D metal–organic frameworks, {[Cd₂(1,4-bdc)₂(bimbb)₂]·H₂O}_n (1), {[Cd₂(4,4′-bpdb)₂(bimbb)(H₂O)₂]} _n (2), [Cd₂(5-Me-1,3-bdc)₂(bimbb)] _n (3), and {[Cd₃(btc)₂(bimbb)(H₂O)₂]·2H₂O} _n (4). Complexes 1–4 were characterized by elemental analysis, IR spectroscopy, powder X-ray powder diffraction, and single-crystal X-ray diffraction. 1 possesses a 3-D framework with 2-D undulated (8,4) layers which are further connected by bimbb pillars. 2 forms a 3-D pillared-layer framework constructed through 2-D undulated (4,4) layers and bimbb pillars. 3 has 1-D ribbons of [Cd₄(5-Me-1,3-bdc)₄] _n which are linked by bimbb to form a 3-D structure. 4 exhibits a 3-D pillared-bilayer framework consisting of (6,3) double-decker [Cd₉(btc)₆(μ-OH₂)₆] _n layers and bimbb pillars. The Schläfli symbols for the four frameworks are (4²·6³·8)(4²·6⁵·8³) (1), (4⁴·6⁶) (2), (4⁴·6²)(4⁶·6⁴) (3), and (6³)(6¹⁰) (4). The photoluminescent properties of 1–4 were also investigated.     

Frameworks Tuned by Different Anions via Charge‐Assisted Weak Hydrogen Bonds

Reactions of Co(ClO₄)₂·6H₂O, Cu(NO₃)₂·3H₂O with 4,4′‐dipyridylsulfide (dps) give rise to coordination polymers {[Co(dps)₂(DMF)₂]·2(ClO₄)·2dps}_n ( 1 ) and {[Cu(dps)₂(DMF)(H₂O)]·(PF₆)·(NO₃)}_n ( 2 ) (DMF = formydimethylamine), respectively. X‐ray diffraction analyses reveal that compound 1 has a one dimensional (1D) chain structure, whereas compound 2 is built of the non‐interpenetrating wave‐like (4, 4) nets. Close inspection of the abundant charge‐assisted weak hydrogen bonds (C‐H···X, X = O, F) between the anions and frameworks in these compounds reveals that the appearance of anion may have a subtle effect on the framework topology. Furthermore, quite few examples of framework holding two different anions only via weak effects as 2 were observed in coordination polymers.     

基于2-硫代巴比妥酸构筑零维原子簇{[Cu6(H2tba)6]·2DMF·xSolvent}、二维层状{[Sc(H2tba)3(DMF)]·2DMF}n和三维网状{[Fe(H2tba)2(H2O)2]·2DMF}n

分别以Cu (ClO₄)₂·6H₂O、Sc (ClO₄)₃·6H₂O和Fe (ClO₄)₃·9H₂O为金属盐,2-硫代巴比妥酸(H₃tba)为配体,通过扩散反应得到了3种不同结构的配合物{[Cu₆(H₂tba)₆]·2DMF·xSolvent}(1)、{[Sc (H₂tba)₃(DMF)]·2DMF}_n(2)和[Fe (H₂tba)₂(H₂O)₂]_n(3),并用红外光谱、元素分析、热重分析和粉末X射线衍射对配合物进行了表征。单晶X射线衍射结构分析表明配合物1是一个具有三方反棱柱构型的六核铜原子簇合物,配合物2是一个具有二维层状结构的化合物,配合物3是一个具有三维网状结构的配位聚合物。配合物1在390 nm光照激发下在735 nm处有强的荧光发射峰。     

基于2,3,5,6-四氟对苯二甲酸构筑的两个超分子网络结构的合成、结构和荧光性质(英文)

在水热条件下合成了基于四氟对苯二甲酸的2个二维微孔配位聚合物{[Cd2(IP)2(tfBDC)2(H2O)2]·H2O}n(1)和{[Mn2(IP)2(tfBDC)2(H2O)2]·H2O}n(2)(tfBDC=2,3,5,6-四氟对苯二甲酸,IP=1-H-咪唑[4,5-f][1,10]-菲咯啉)。二维层状结构是44-网状结构,三维超分子结构是由氢键连接相邻的二维层状结构而形成的。2个配位聚合物均用元素分析、热重分析(TGA)、粉末衍射(PXRD)、红外光谱(FT-IR)进行了表征,且对配合物1的荧光性质进行了详细的分析。     

一系列由柔性N,N'-双(3-吡啶甲基)胺构筑的螺旋配合物的合成、结构和性质

合成和表征了5个螺旋配位聚合物{[Cu(Hbpma)(H₂O)₄]₂(SO₄)₃·3.5H₂O}_n (1)、{[Ni(Hbpma)(H₂O)₄]₄(SO₄)₆·10.75H₂O}_n (2)、{[Mn(Hbpma)(H₂O)₄](SO₄)_1.5·3H₂O}_n (3)、{[Zn(Hbpma)(H₂O)₄]₄(SO₄)₆·4H₂O·4CH₃OH}n (4)和{[Cu(Hbpma)2(H₂O)₂](SO₄)₂·9H₂O}_n (5), 其中bpma代表N,N'-双(3-吡啶甲基)胺。晶体结构分析表明配合物1~4为一维链状结构, 配合物5为二维层状结构, 其中金属离子由质子化的bpma配体桥连。值得注意的是, 采取反-反式构象的柔性bpma配体使得配合物1和2为假螺旋链结构, 配合物3和4为螺旋链结构, 配合物5为螺旋层结构。同时研究了配合物的磁性和热稳定性。     

基于半刚性三角形羧酸配体构筑的配位聚合物的合成,结构及其荧光性质

通过使用一个半刚性的多齿羧酸配体3,3',3"-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H₃L),在溶剂热条件下合成了4个配位聚合物{[Cd₃(L)₂(H₂O)₂]·5DMF·6H₂O}_n (1),{[Co₃(L)₂(H₂O)₂]·2DMF·6H₂O}_n (2),{[Mn₃(L)₂(H₂O)₂]·3DMF·6H₂O}_n (3),{[Zn₃(L)₂(H₂O)₂]·5DMA·5H₂O}_n (4),并通过X射线单晶衍射,热重分析对配合物结构进行了表征。4个化合物都是同构的,由沙漏型的M₃簇和L^3-配体作为次级结构单元,从而给出了一个金属-有机纳米笼的三维结构,从拓扑学的观点看,4个配合物的结构可以看作是三节点的(3,3,6)-连接的网络。荧光光谱测试表明配合物1和4在激发波长为272 nm下,在385 nm处显示了强的宽发射峰。荧光传感测试结果表明,配合物1是一种潜在的硝基苯类化合物的传感材料。     

Three lanthanide coordination polymers with nitrilotriacetic acid: hydrothermal syntheses,crystal structures and fluorescent property

Hydrothermal reactions of Sm₂O₃, Gd(ClO₄)₃?·?6H₂O and Tb(ClO₄)₃?·?6H₂O with nitrilotriacetic acid, give rise to three lanthanide coordination polymers, {[Sm(NTA)(H₂O)₂]?·?H₂O} _n (1), {[Gd(NTA)(H₂O)]?·?H₂O} _n (2) and {[Tb(NTA)(H₂O)]?·?H₂O} _n (3). Their solid-state structures have been characterized by elemental analysis, and IR spectroscopy. X-ray single-crystal diffraction analyses indicated that 2 and 3 are isomorphous three-dimensional coordination polymers with eight-coordinate Gd(III) (or Tb(III)), while 1 forms a two-dimensional coordination polymer containing nine-coordinate Sm(III). The photophysical properties of 3 have been studied with excitation and emission spectra, which exhibit strong green emission.     

Crystal engineering of Cd(II) metal–organic frameworks bridged by dicarboxylates and N-donor coligands

Two new metal–organic coordination polymers, {[Cd₄(bpea)₄(IP)₈]?·?6H₂O} _n (1) and {[Cd_1.5(suc)_1.5(IP)_1.5]?·?4H₂O} _n (2) (bpea?=?biphenylethene-4,4′-dicarboxylate, H₂suc?=?succinic acid and IP?=?1H-imidazo[4,5-f][1,10]-phenanthroline), have been obtained through two types of dicarboxylate linkers. Complex 1 contains a neutral 2-D puckered sheet that is interdigitated by neutral 1-D zigzag chains. Compound 2 shows a 2-D (4,4) net, which is extended into a 3-D supramolecular framework by weak aromatic interactions. The different structures demonstrate the effect of the dicarboxylate ligands on the formation of such coordination architectures. The fluorescence property of the two complexes was also investigated.     

Metal‐ and Substituent‐Dependent Structural Diversity in ­Cobalt and Nickel Isophthalate Coordination Polymers with Bis(4‐pyridylformyl)piperazine Tethers

Hydrothermal reactions of nickel or cobalt nitrate with the dipyridylamide ligand bis(4‐pyridylformyl)piperazine (4‐bpfp) and either 5‐methoxyisophthalate (H₂omeip) or 5‐methylisophthalate (H₂mip) afforded a series of coordination polymers that were structurally characterized by single‐crystal X‐ray diffraction. Different synthetic conditions afforded the 1D chain phase {[Ni(Homeip)₂(H₂omeip)(bpfp)] · 2H₂O}_n ( 1 ) or the mutually inclined interpenetrated (4, 4) grid system in {[Ni(omeip)(bpfp)(H₂O)] · 2H₂O}_n ( 2 ). The analogous cobalt phase {[Co(omeip)(bpfp)] · 3H₂O}_n ( 3 ) lacks bound water molecules, which enforces a non‐interpenetrated (4, 4) grid structure based on {Co₂(OCO)₂} dinuclear clusters. Similar clusters are seen in {[Co(mip)(bpfp)(H₂O)₂] · 3.5H₂O}_n ( 4 ), which manifests a 1D ribbon structural motif. Its nickel congener {[Ni(Hmip)₂(bpfp)(H₂O)₂] · 2H₂mip}_n ( 5 ) also shows a 1D chain motif. A variable temperature magnetic susceptibility study indicates antiferromagnetic coupling within the dimeric units in 3 and 4 concomitant with single ion effects. Additionally, thermal degradation properties of these new materials are described.     

Substituent Dependent Dimensionality in Luminescent Zinc Isophthalate Coordination Polymers Containing Bis(3‐pyridylmethyl)piperazine

Divalent zinc coordination polymers containing bis(3‐pyridylmethyl)piperazine (3‐bpmp) and isophthalate ligands have been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction. {[Zn(ip)(H3‐bpmp)]ClO₄·4H₂O}_n ( 1 , ip = isophthalate) has twofold parallel interpenetrated (4,4) grid cationic coordination polymer nets, with unligated perchlorate ions and intriguing infinite water molecule chains. {[Zn₂(NO₂ip)₃(H₂3‐bpmp)(H₂O)₅]·3H₂O}_n ( 2 , NO₂ip = 5‐nitroisophthalate) exhibits a supramolecular lattice built from 1D chain motifs, revealing a significant dependence of topology on the steric bulk of the dicarboxylate ligand. Luminescent properties for 1 and 2 are also reported.     

Syntheses,Crystal Structures,and Magnetic Properties of Three 1D Chain Metal–Nitroxide Complexes Bridged by ­Flexible Dicarboxylate Anions

Three new one‐dimensional (1D) chain metal–nitroxide complexes {[Cu(NIT4Py)₂(suc)(H₂O)] · 3H₂O}_n ( 1 ), {[Cd(NIT4Py)₂(suc)(H₂O)] · [Cd(NIT4Py)₂(suc)(H₂O)₂] · 3H₂O}_n ( 2 ), and {[Zn(NIT4Py)(glu)(H₂O)] · H₂O}_n ( 3 ) [NIT4Py = 2‐(4′‐pyridyl)‐4, 4, 5, 5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide, suc = succinate anion and glu = glutarate anion] were synthesized and structurally characterized. Single‐crystal X‐ray analyses indicate that the three complexes crystallize in neutral 1D chains in which the metal‐nitroxide units are linked by flexible dicarboxylate anions. The succinate anions only adopt trans configuration in complexes 1 and 2 , whereas the glutarate anion has gauche/anti conformation in complex 3 . Magnetic measurements show that complex 1 exhibits weak antiferromagnetic interactions between the copper ions and the nitroxides.