Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4-dicarboxylate: Effect of Lanthanide Contraction on Structures

Introduction Recently, the coordination polymers based on dicar-boxylic acid have been studied extensively for their importance as promising materials.1-7 So the rational design and synthesis of novel coordination polymers with useful functions attract considerable attention. As well known, the design of extended structure with po-tential applications can be realized by starting with connecting ligands capable of binding metal centers strongly and predictably to afford the structures with expe…     

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

Synthesis,Crystal Structure and Thermal Behavior of a New 2D Barium（Ⅱ） Coordination Polymer with 1H-benzimi-dazole-5,6-dicarboxylate as the Single Ligand

The self-assembly of 1H-benzimidazole-5,6-dicarboxylic acid with barium chloride under hydrothermal conditions afforded a new 2D coordination polymer,[Ba2(L)(HL)Cl]n(1,L = 1H-benzimidazole-5,6-dicarboxylate),which was characterized by elemental analysis,infrared spectroscopy,thermogravimetric analysis,and single-crystal X-ray diffraction.Compound 1 is of monoclinic system,space group P21/c with a = 10.0145(6),b=25.6854(15),c=7.3116(4) ?,β = 99.4980(10)°,V = 1854.95(19)3,C18H9Ba2ClN4O8,Z = 4,Mr=719.42,Dc = 2.576 g/cm3,μ(MoKα) = 4.427 mm-1,F(000) = 1352,the final R = 0.0202 and wR=0.0465 for 3051 observed reflections with I > 2σ(I).It exhibits an interesting two-dimensional network structure and high thermal stability(up to 420 ℃).     

Two New Coordination Polymers Assembled with a Functionalized Ligand：Syntheses and Crystal Structures

Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).     

Syntheses and Crystal Structures of Two Coordination Polymers of Cobalt and Cadmium Assembled by 4,4ˊ-(Ethane-1,2-diyldioxy)dibenzoic Acid

Two new metal-organic coordination polymers [Co0.5（Heoba）（bib）0.5]2n（1） and [Cd（eoba）（phen）]n（2）（H2eoba = 4,4-（ethane-1,2-diyldioxy）dibenzoic acid, bib = 1,4-bis（imidazol-1-yl）-butane, phen = 1,10-phenanthroline） have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. Complex 1 is a 2D network structure, and complex 2 exhibits a 3D network structure. Moreover, the luminescent property of complex 2 has been investigated in the solid state.     

1D Lanthanide Coordination Polymers Based on 3-（Pyridin-4,yl）benzoic Acid： Syntheses, Structures and Luminescent Properties

Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(H2O)2· H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoclinic system, space group P1. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Two New Coordination Polymers Containing Metal-carboxylate Helix

Two novel compounds, {[Cd(nbdc)(bpp)(H2O)]·H2O}n 1 and {[Cd(nbdc)(dpds)-(H2O)]·H2O}n 2(H2nbdc = 4-nitro-1,2-benzenedicarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane and dpds = 4,4ˊ-dipyridyldisulfide), were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), fluorescent analysis and single-crystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a = 14.4370(17), b = 8.4090(10), c = 19.168(2) , β = 104.5050(10)°, V = 2252.8(5) 3, Dc = 1.639 g/cm3, Mr = 555.81, Z = 4, F(000) = 1120, μ = 1.022 mm-1, the final R = 0.0269 and wR = 0.0599 for 16656 observed reflections with I 2σ(I). 2 is isostructural to 1 with a = 14.4175(11), b = 8.4737(7), c = 18.0120(14) , β = 106.7220(10)°, V = 2107.5(3)3, Dc = 1.821 g/cm3, Mr = 577.85, Z = 4, F(000) = 1152, μ = 1.287 mm-1, the final R = 0.0280 and wR = 0.0705 for 15136 observed reflections with I 2σ(I). Both complexes present intimately related structures featuring infinite Cd-carboxylate helix of [CdⅡ(nbdc)(H2O)]n connected by bpp(or dpds) molecule to produce the 2D layer frameworks.     

Synthesis,Crystal Structures and Magnetic Properties of Cobalt（II） and Manganese（II） Coordination Polymers Constructed from 5-（Pyridin-4-yl）isophthalate Ligands

Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

A new family of lanthanide coordination polymers based on 3,3′‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoate: synthesis,crystal structures and magnetic and luminescence properties

Six two‐dimensional (2D) coordination polymers (CPs), namely, poly[{μ₅‐3,3‐[(5‐carboxylato‐1,3‐phenylene)bis(oxy)]dibenzoato‐κ⁶O¹:O^1′:O³,O^3′:O⁵:O^5′}bis(N,N‐dimethylformamide‐κO)lanthanide(III)], [Ln(C₂₁H₁₁O₈)(C₃H₇NO)₂]_n, with lanthanide/Ln = cerium/Ce for CP1 , praseodymium/Pr for CP2 , neodymium/Nd for CP3 , samarium/Sm for CP4 , europium/Eu for CP5 and gadolinium/Gd for CP6 , have been prepared by solvothermal methods using the ligand 3,3′‐[(5‐carboxy‐1,3‐phenylene)bis(oxy)]dibenzoic acid (H₃cpboda) in the presence of Ln(NO₃)₃. The complexes were characterized by single‐crystal X‐ray and powder diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis (TGA). All the structures of this family of lanthanide CPs are isomorphous with the triclinic space group P and reveal that they have the same 2D network based on binuclear Ln^III units, which are further extended via interlayer C—H…π interactions into a three‐dimensional supramolecular structure. The carboxylate groups of the cpboda^3? ligands link adjacent Ln^III ions and form binuclear [Ln₂(RCOO)₄] secondary building units (SBUs), in which each binuclear Ln^III SBU contains four carboxylate groups from different cpboda^3? ligands. Moreover, with the increase of the rare‐earth Ln atomic radius, the dihedral angles between the aromatic rings gradually increase. Magnetically, CP6 shows weak antiferromagnetic coupling between the Gd^III ions. The solid‐state luminescence properties of CP2 , CP5 and CP6 were examined at ambient temperature and CP5 exhibits characteristic red emission bands derived from the Eu³⁺ ion (CIE 0.53, 0.31), with luminescence quantum yields of 22%. Therefore, CP5 should be regarded as a potential optical material.     

A one‐dimensional cobalt(II) coordination polymer based on 2,4′‐oxydibenzoic acid: poly[[[diaquabis[2‐(4‐carboxyphenoxy)benzoato‐κO1]cobalt(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] dihydrate]

The reaction of CoSO₄ with 2,4‐oxydibenzoic acid (H₂oba) and 4,4′‐bipyridine (bipy) under hydrothermal condition yielded a new one‐dimensional cobalt(II) coordination polymer, {[Co(C₁₄H₉O₅)₂(C₁₀H₈N₂)(H₂O)₂]·2H₂O}_n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, magnetic properties and single‐crystal X‐ray diffraction. The Co^II ions are connected by bipy ligands into infinite one‐dimensional chains. The Hoba⁻ ligands extend out from the two sides of the one‐dimensional chain. O—H...O hydrogen bonding extends these chains into a two‐dimensional supramolecular architecture.     

Synthesis and X‐ray single‐crystal structure study of 5,5′‐bis(silyl)‐functionalized 3,3′‐dibromo‐2,2′‐dithiophenes

A high‐yield synthesis toward 5,5′‐bis(silyl)‐functionalized 3,3′‐dibromo‐2,2′‐dithiophenes with very efficient work‐up procedure is presented. The molecular structures of two silyl functionalized dibromo‐dithiophenes in the solid state have been determined to investigate the structural influences of different functional groups on the degree of π‐conjugation within the dithiophene moieties, as well as their packing properties. The planar alignment of the tert‐butyldimethylsilyl‐functionalized dibromo‐dithiophene shows a significantly higher degree of conjugation of the π‐system with a more favorable molecular packing than the skewed arrangement of the triisopropylsilyl‐substituted species. Copyright © 2005 John Wiley & Sons, Ltd.     

几种三维镧系配位聚合物的合成、结构表征及其性质测定

在水热条件下合成了四个氨三乙酸配合物[Ln(NTA)(H2O)]n(Ln=Sm(III)、Gd(III)、Dy(III)和Er(III);NTA=氨三乙酸),分别标记为1、2、3和4;利用元素分析、红外光谱和X射线单晶衍射等对其进行了结构表征.结果表明,配合物1-4同晶同构,中心原子采取N1O7的配位模式形成扭曲的十二面体几何构型.配合物以菱形四面体Ln8C14O28为基本构筑块,通过O—C—O和氢键形成有序的三维结构.此外,四个配合物均存在镧系收缩效应;配合物1显示出反铁磁性,配合物2对Hg2+有良好的荧光选择性.     

Crystallographic report: A three‐dimensional coordination polymer: [Zn6(btc)4(4,4′‐bipy)5]n (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine)

The three‐dimensional (3D) coordination polymer [Zn₆(btc)₄(4,4′‐bipy)₅]_n ( 1 ) (btc = 1,2,4‐benzenetricarboxylate; 4,4′‐bipy = 4,4′‐bipyridine) has been prepared hydrothermally. The zinc(II) centers in 1 are bridged by btc ligands to form a trinuclear subunit, which is further linked by 4,4′‐bipy and btc ligands to construct the 3D coordination architecture. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,structural characterization and computational studies of catena‐poly[chlorido[μ3‐(pyridin‐1‐ium‐3‐yl)phosphonato‐κ3O:O′:O′′]zinc(II)]

Coordination polymers are constructed from two basic components, namely metal ions, or metal‐ion clusters, and bridging organic ligands. Their structures may also contain other auxiliary components, such as blocking ligands, counter‐ions and nonbonding guest or template molecules. The choice or design of a suitable linker is essential. The new title zinc(II) coordination polymer, [Zn(C₅H₅NO₃P)Cl]_n , has been hydrothermally synthesized and structurally characterized by single‐crystal X‐ray diffraction and vibrational spectroscopy (FT–IR and FT–Raman). Additionally, computational methods have been applied to derive quantitative information about interactions present in the solid state. The compound crystallizes in the monoclinic space group C 2/c . The four‐coordinated Zn^II cation is in a distorted tetrahedral environment, formed by three phosphonate O atoms from three different (pyridin‐1‐ium‐3‐yl)phosphonate ligands and one chloride anion. The Zn^II ions are extended by phosphonate ligands to generate a ladder chain along the [001] direction. Adjacent ladders are held together via N—H…O hydrogen bonds and offset face‐to‐face π–π stacking interactions, forming a three‐dimensional supramolecular network with channels. As calculated, the interaction energy between the neighbouring ladders is −115.2 kJ mol⁻¹. In turn, the cohesive energy evaluated per asymmetric unit‐equivalent fragment of a polymeric chain in the crystal structure is −205.4 kJ mol⁻¹. This latter value reflects the numerous hydrogen bonds stabilizing the three‐dimensional packing of the coordination chains.     

Potassium 1,1′‐Dinitramino‐5,5′‐bistetrazolate: A Primary Explosive with Fast Detonation and High Initiation Power

Adequate primary explosives such as lead azide mostly contain toxic ingredients, which have to be replaced. A new candidate that shows high potential, potassium 1,1′‐dinitramino‐5,5′‐bistetrazolate (K₂DNABT), was synthesized by a sophisticated synthetic procedure based on dimethylcarbonate and glyoxal. It was intensively characterized for its chemical (X‐ray diffraction, EA, NMR and vibrational spectroscopy) and physico‐chemical properties (sensitivity towards impact, friction, and electrostatic, DSC). The obtained primary explosive combines good thermal stability with the desired mechanical stability. Owing to its high heat of formation (326 kJ mol^?1) and density (2.11 g cm^?3), impressive values for its detonation velocity (8330 m s^?1) and pressure (311 kbar) were computed. Its superior calculated performance output was successfully confirmed and demonstrated by different convenient energetic test methods.     

Anion‐directed assemblies of europium(III) coordination polymers based on 1H‐benzimidazole‐5,6‐dicarboxylate: structures and luminescence properties

Two europium(III) coordination polymers (CPs), namely, poly[[diaquabis(μ₄‐1H‐benzimidazole‐5,6‐dicarboxylato‐κ⁶N³:O⁵,O^5′:O⁵,O⁶:O^6′)(μ₂‐oxalato‐κ⁴O¹,O²:O^1′,O^2′)dieuropium(III)] dihydrate], {[Eu₂(C₉H₄N₂O₄)₂(C₂O₄)(H₂O)₂]·2H₂O}_n ( 1 ), and poly[(μ₃‐1H‐benzimidazol‐3‐ium‐5,6‐dicarboxylato‐κ⁵O⁵:O^5′,O⁶:O⁶,O^6′)(μ₃‐sulfato‐κ³O:O′:O′′)europium(III)], [Eu(C₉H₅N₂O₄)(SO₄)]_n ( 2 ), have been synthesized via the hydrothermal method and structurally characterized. CP 1 shows a three‐dimensional network, in which the oxalate ligand acts as a pillar, while CP 2 has a two‐dimensional network based on a europium(III)–sulfate skeleton, further extended into a three‐dimensional framework by hydrogen‐bonding interactions. The structural diversity in the two compounds can be attributed to the different acidification abilities and geometries of the anionic ligands. The luminescence properties of 1 display the characteristic europium red emission with CIE chromaticity coordinates (2/3, 0.34). Interestingly, CP 2 shows the characteristic red emission with CIE chromaticity coordinates (0.60, 0.34) when excited at 280 nm and a near‐white emission with CIE chromaticity coordinates (0.38, 0.29) when excited at 340 nm.     

Two‐dimensional ZnII and one‐dimensional CoII coordination polymers based on benzene‐1,4‐dicarboxylate and pyridine ligands

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H₂BDC) and pyridine (py) with Zn^II or Co^II yielded two new coordination polymers, namely, poly[(μ₄‐benzene‐1,4‐dicarboxylato‐κ⁴O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C₈H₄O₂)(C₅H₅N)]_n, (I), and catena‐poly[aqua(μ₃‐benzene‐1,4‐dicarboxylato‐κ³O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C₈H₄O₂)(C₅H₅N)₂(H₂O)]_n, (II). In compound (I), the Zn^II cation is five‐coordinated by four carboxylate O atoms from four BDC²⁻ ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two Zn^II ions to form centrosymmetric paddle‐wheel‐like Zn₂(μ₂‐COO)₄ units, which are linked by the benzene rings of the BDC²⁻ ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co₂(μ₂‐COO)₂ units. The Co^II cations are bridged by BDC²⁻ ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC²⁻ ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.