Synthesis, Crystal Structure, Luminescence, and Magnetic Properties of a New 4d–4f Heterometallic Architecture Based on Pyridine-3,4-Dicarboxylic Acid

A 4d–4f heterometallic coordination polymer, [AgEu(pydc)₂]·2H₂O (1) (H₂pydc = pyridine-3,4-dicarboxylic acid), has been synthesized under hydrothermal conditions, and further characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features a three-dimensional framework containing one-dimensional (1D) channels occupied by free water molecules, which is constructed from 1D inorganic heterometallic chains and linear pydc linkers. After removal of the water molecules from complex 1, the remaining material has high thermal stability. Moreover, the photoluminescence, and magnetic properties of 1 were also investigated.     

{[Eu(ox)(H2O)4]·[CuBr(2‐pzc)2]·4H2O}: Hydrogen Bonding Directed Assembly to Supramolecular Network

A new 3d–4f heterometallic coordination framework, {[Eu(ox)(H₂O)₄] · [CuBr(2‐pzc)₂] · 4H₂O} ( 1 ) [ox = oxalate; 2‐pzc = pyrazine‐2‐carboxylate] was synthesized and characterized by elemental analysis, IR spectroscopy and thermal analysis, as well as single‐crystal X‐ray diffraction. Complex 1 represents one 3D supramolecular heterometallic coordination framework that is assembled from rare lanthanide‐ox anionic chains and CuBr(2‐pzc)₂ cationic units through hydrogen bonds.     

1-D Ln–Ag (Ln = Eu; Tb) heterometallic coordination polymers with pyridine-2,6-dicarboxylate as the single ligand: Synthesis,crystal structures,and luminescence

Two new 4d–4f heterometallic coordination polymers [AgLn(pydc)₂(H₂O)₃] · x(H₂O) [Ln = Eu, x = 1.25 (1); Ln = Tb, x = 1.25 (2); pydc = 2,6-pyridinedicarboxylate] have been synthesized and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. Both structures display the same unusual 1-D heterometallic coordination polymer based on Ln building blocks and Ag ions. Thermal stabilities and luminescent properties of 1 and 2 are presented.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of two 3d‐4f Heterometallic Coordination Polymers

Two new 3d‐4f heterometallic coordination polymers, [LnCu(nic)₂(ox)]·2H₂O (Ln = Sm( 1 ), Dy ( 2 ), ox = oxalate anion, Hnic = nicotinic acid) were synthesized and characterized by elementary analysis, IR spectroscopy and thermogravimetric analysis, as well as single‐crystal X‐ray diffraction. The two structures exhibit the same unusual 3D microporous heterometallic coordination frameworks with 13.7 % voids occupied by guest water molecules.     

2D LnIII(Nd/La)‐AgI Heterometallic and TmIII Homometallic Coordination Polymers Based on Pyridine Dicarboxylate ­Ligands

Two 2D 4d‐4f heterometallic coordination polymers, [LnAg(Py26DC)₂(H₂O)₃] · 3H₂O [Ln = Nd ( 1 ), La ( 2 ); H₂Py26DC = pyridine‐2,6‐dicarboxylic acid], and one 2D lanthanide homometallic coordination polymer, [Ln(Py25DC)(ox)_0.5(H₂O)₂] [Ln = Tm ( 3 ); H₂Py25DC = pyridine‐2,5‐dicarboxylic acid; ox = oxalate], were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single‐crystal X‐ray diffraction analysis. Both complexes 1 and 2 are isostructural and exhibit 3‐connected 2D heterometallic layer structures with the Schläfli symbol of (8² · 10), whereas complex 3 represents an extended 2D homometallic network structure with (4,4) topology.     

Synthesis and characterization of two isostructural 3d–4f coordination compounds based on pyridine‐2,6‐dicarboxylic acid and 4,4′‐bipyridine

The design and synthesis of 3d–4f heterometallic coordination polymers have attracted much interest due to the intriguing diversity of their architectures and topologies. Pyridine‐2,6‐dicarboxylic acid (H₂pydc) has a versatile coordination mode and has been used to construct multinuclear and heterometallic compounds. Two isostructural centrosymmetric 3d–4f coordination compounds constructed from pyridine‐2,6‐dicarboxylic acid and 4,4′‐bipyridine (bpy), namely 4,4′‐bipyridine‐1,1′‐diium diaquabis(μ₂‐pyridine‐2,6‐dicarboxylato)tetrakis(pyridine‐2,6‐dicarboxylato)bis[4‐(pyridin‐4‐yl)pyridinium]cobalt(II)dieuropium(III) octahydrate, (C₁₀H₁₀N₂)[CoEu₂(C₁₀H₉N₂)₂(C₇H₃NO₄)₆(H₂O)₂]·8H₂O, (I), and 4,4′‐bipyridine‐1,1′‐diium diaquabis(μ₂‐pyridine‐2,6‐dicarboxylato)tetrakis(pyridine‐2,6‐dicarboxylato)bis[4‐(pyridin‐4‐yl)pyridinium]cobalt(II)diterbium(III) octahydrate, (C₁₀H₁₀N₂)[CoTb₂(C₁₀H₉N₂)₂(C₇H₃NO₄)₆(H₂O)₂]·8H₂O, (II), were synthesized under hydrothermal conditions and characterized by IR and fluorescence spectroscopy, thermogravimetric analysis and powder X‐ray diffraction. Both compounds crystallize in the triclinic space group P. The Eu^III and Tb^III cations adopt nine‐coordinated distorted tricapped trigonal–prismatic geometries bridged by three pydc^2? ligands. The Co^II cation has a six‐coordination environment formed by two pydc^2? ligands, two bpy ligands and two coordinated water molecules. Adjacent molecules are connected by π–π stacking interactions to form a one‐dimensional chain, which is further extended into a three‐dimensional supramolecular network by multipoint hydrogen bonds.     

Syntheses,Structures, and Electrochemical Properties of Two Bis‐triazole‐bis‐amide‐based Copper(II) Pyridine‐2,3‐dicarboxylate Coordination Polymers

Abstract. Two bis‐triazole‐bis‐amide‐based copper(II) pyridine‐2,3‐dicarboxylate coordination polymers (CPs), [Cu(2,3‐pydc)(dtb)_0.5(DMF)] · 2H₂O ( 1 ) and [Cu(2,3‐pydc)(dth)_0.5(DMF)] · 2H₂O ( 2 ) (2,3‐H₂pydc = pyridine‐2,3‐dicarboxylic acid, dtb = N,N′‐bis(4H‐1,2,4‐triazole)butanamide, and dth = N,N′‐bis(4H‐1,2,4‐triazole)hexanamide), were synthesized under solvothermal conditions. CPs 1 and 2 show similar two‐dimensional (2D) structures. In 1 , the 2,3‐pydc anions bridge the Cu^II ions into a one‐dimensional (1D) chain. Such 1D chains are linked by the dtb ligands to form a 2D layer. The adjacent 2D layers are extended into a three‐dimensional (3D) supramolecular architecture by hydrogen‐bonding interactions. The electrochemical properties of 1 and 2 were investigated.     

Ag(I)配位聚合物[Ag2(bpp)2(H2O)]·pydc·7H2O的合成、表征及性质研究

水热合成了基于吡啶-3,5-二羧酸(H2pydc)的含Ag(I)配位聚合物 [Ag2(bpp)2(H2O)]·pydc·7H2O (1) (其中bpp = 1,3-双(4-吡啶)丙烷)。X射线单晶结构分析表明,在一维化合物1中,发现了包含(H2O)12水簇单元的二维氢键层状结构。有趣的是,在该二维层中, 每个pydc2-阴离子作为“桥”连接了两个(H2O)12单元和两个自由水分子。另外,对化合物1的荧光、热重、粉末衍射等也进行了研究和讨论。     

A novel three‐dimensional heterometallic coordination polymer: poly[[hexaaquabis[μ3‐3,5‐dicarboxylatopyrazolato‐κ5O3,N2:N1,O5:O5′](μ2‐oxalato‐κ4O1,O2:O1′,O2′)copper(II)dierbium(III)] trihydrate]

The title novel heterometallic 3d–4f coordination polymer, {[CuEr₂(C₅HN₂O₄)₂(C₂O₄)(H₂O)₆]·3H₂O}_n, has a three‐dimensional metal–organic framework composed of two types of metal atoms (one Cu^II and two Er^III) and two types of bridging anionic ligands [3,5‐dicarboxylatopyrazolate(3−) (ptc³⁻) and oxalate]. The Cu^II atom is four‐coordinated in a square geometry. The Er^III atoms are both eight‐coordinated, but the geometries at the two atoms appear different, viz. triangular dodecahedral and bicapped trigonal prismatic. One of the oxalate anions is located on a twofold axis and the other lies about an inversion centre. Both oxalate anions act as bis‐bidentate ligands bridging the latter type of Er atoms in parallel zigzag chains. The pdc³⁻ anions act as quinquedentate ligands not only chelating the Cu^II and the triangular dodecahedral Er^III centres in a bis‐bidentate bridging mode, but also connecting to Er^III centres of both types in a monodentate bridging mode. Thus, a three‐dimensional metal–organic framework is generated, and hydrogen bonds link the metal–organic framework with the uncoordinated water molecules. This study describes the first example of a three‐dimensional 3d–4f coordination polymer based on pyrazole‐3,5‐dicarboxylate and oxalate, and therefore demonstrates further the usefulness of pyrazoledicarboxylate as a versatile multidentate ligand for constructing heterometallic 3d–4f coordination polymers with interesting architectures.     

Hydrothermal Syntheses and Structural Studies of Lanthanide Coordination Polymers Involving In‐Situ Decarboxylation and their Luminescence Properties

Lanthanide coordination polymers with the formula [Ln(pydc)₂]·H₂O (Ln = La, 1 ; Nd, 2 ; pydc = 3,4‐pyridinedicarboxylate) and [Ln(pydc)(ina)(H₂O)₂] (Ln = Sm, 3 ; Eu, 4 ; Tb, 5 ; Dy, 6 ; pydc = 3,4‐pyridinedicarboxylate, ina = isonicotinate) were synthesized by treating Ln^III nitrates with 3,4‐pyridinedicarboxylic acid under hydrothermal conditions. Single‐crystal and powder X‐ray diffraction studies indicate that these lanthanide coordination polymers adopt two different structures. The lighter lanthanide compounds 1 and 2 consist of extended two‐dimensional layer structures with the thickness of ca. 1.7 nm. While the heavier lanthanide compounds 3 ‐ 6 have pydc‐bridged double chain structures with one chelating carboxylate group of ina ligand and two water molecules on each metal center. Interestingly, decarboxylation occurred and pydc was partially transformed into ina in the hydrothermal reactions of 3 ‐ 6 . The fluorescence activities of compounds 4 and 5 are reported.     

A 3d‐4f Complex Constructed by the Assembly of a Cationic Template, [Cu(en)2]2+, and a 3D Anionic Coordination Polymer, [Sm2(C2O4)3(C5O5)(H2O)2]2–

A three‐dimensional (3D) 3d‐4f complex, [Cu(en)₂][Sm₂(C₅O₅)(C₂O₄)₃(H₂O)₂] · 8H₂O ( 1 ) (en = ethylenediamine, C₅O₅^2– = dianion of 4,5‐dihydroxycyclopent‐4‐ene‐1,2,3‐trione), were prepared via the in‐situ ring‐opening oxidation reaction of croconate in the presence of the template‐directed complex, [Cu(en)₂]²⁺ cation. The structural characterization determined by X‐ray diffraction determination reveals that the 3D anionic coordination polymer of [Sm₂(C₂O₄)₃(C₅O₅)(H₂O)₂]^2– in 1 can be describe in terms of in‐plane 2D honeycomb‐like [Sm₂(C₂O₄)₃] layered frameworks bridged by oxalate with bis‐chelating mode, being mutually interlinked via the bridge of μ_1,2,3,4‐croconate ligands with bis‐chelating coordination mode to complete the 3D open framework, which gives rise to 1D channels with pore size of 14.023 × 11.893 Å (longest atom–atom contact distances) along the b axis. The structure‐directing complex, [Cu(en)₂]²⁺, and solvated water molecules are resided into these honeycomb‐type hexagonal channels. The thermal stability of 1 was further studied by TGA and in‐situ powder X‐ray diffraction measurement.     

Hydrothermal Syntheses,Crystal Structures and Properties of Two Novel 3‐D Lanthanide(III) Coordination Polymers Constructed with Mixed Heterocyclic Carboxylic Acid

The hydrothermal reactions of Ln₂O₃ (Ln = Nd and Eu) with pyridine‐2,5‐dicarboxylic acid (H₂pydc) resulted in the formation of two isomorphic three‐dimensional (3D) polymeric Ln^III complexes, [Ln(pydc)(nic)·H₂O]_n (Ln = Nd( 1 ) and Eu( 2 )), in which nic (nicotinate; also named as pyridine‐2‐carboxylic acid) might have been formed from the pydc ligands through the C–C bond cleavage and CO₂ molecules releasing. Pydc ligands bridge lanthanide centers to form the three‐dimensional framework featuring hexagonal channels along the axis a which are occupied by bridging nic anions and mono‐coordinated water molecules. From the topological point of view, two three‐dimensional nets are binodal with six‐ and three‐connected nodes, which display a distorted rutile (4.6²)₂(4²·6¹⁰·8³) topology. Magnetic measurements (2‐300 K) reveal that all polymers possess weak antiferromagnetic property. A strong fluorescence emission spectrum of compound 2 was observed.     

Synthesis, structure and thermogravimetric analysis of Ni–Cd and Cu–Cd heterometallic complexes based on flexible carboxylate ligands

Two 3d–4d heterometallic coordination polymers, namely NiCd(mal)₂(H₂O)₄ (1) and [CuCd(bicH₂)(NO₃)Cl₂(H₂O)]?H₂O (2) [H₂mal = malonic acid, bicH₃ = N,N-bis(2-hydroxyethyl) glycine], have been synthesized under mild conditions and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrophotometry. Complex 1 is a Ni–Cd heterometallic polymer with 2D extended structure bridged by the mal^2? groups. Complex 2 displays an intriguing 3D Cu–Cd architecture and is the first 3d–4d heterometallic bicinate complex. The TG analyses of both complexes are reported.     

Heterometallic SrII‐MII (M=Co,Ni, Zn and Cu) Coordination Polymers: Synthesis,Temperature‐Dependent Structural Transformation,and Luminescent and Magnetic Properties

The use of pyridine‐2,4‐dicarboxylic acid (H₂pydc) in the construction of Sr^II and Sr^II‐M^II (M=Co, Ni, Zn and Cu) coordination polymers is reported. Eight complexes, that is, [Sr(pydc)H₂O]_n ( 1 ), [MSr(pydc)₂(H₂O)₂]_n (M=Co ( 2 ), Ni ( 3 ), Zn ( 4 )), [ZnSr(pydc)₂(H₂O)₇]_n?4 nH₂O ( 5 ), [SrCu(pydc)₂]_n ( 6 ), [SrCu(pydc)₂(H₂O)₃]_n?2 nH₂O ( 7 ), and [Cu₃Sr₂(pydc)₄(Hpydc)₂(H₂O)₂]_n ( 8 ), have been synthesized via dexterously choosing the appropriate strontium sources and transition metal salts, and rationally controlling the temperature of the reaction systems. Complexes 1 , 2 ( 3 , 4 ), 6 , and 8 display four types of 3‐D framework structures. Complexes 5 and 7 exhibit a 2‐D network and a 1‐D chain structure, respectively. The 2‐D complex 7 can be reversibly transformed into 3‐D compound 6 through temperature‐induced solvent‐mediated structural transformation. The luminescent property studies indicated that complex 1 shows a strong purple luminescent emission and 4 exhibits a strong violet luminescence emission. The magnetic properties of 2 , 3 , and 8 were also studied. Antiferromagnetic M^II???M^II interactions were determined for these complexes.     

Synthesis,Crystal Structure and Magnetic Properties of a Novel Heterobimetallic Rhenium(IV)–Dysprosium(III) Chain

The use of the mononuclear rhenium(IV) precursor [ReBr₅(H₂pydc)]^? (H₂pydc=3,5‐pyridinedicarboxylic acid) as a metalloligand towards dysprosium(III) afforded the first heterobimetallic Re^IV–Dy^III complex. Crystal structures and static and dynamic magnetic properties of both rhenium‐containing species are reported herein. The 5d–4f compound shows an extended 1D structure and the AC magnetic measurements reveal frequency dependence at low temperature suggesting slow relaxation of the magnetization.     

A 3-D pillar-layered coordination polymer {[EuCu(C2O4)(na)2] · 2H2O} n : synthesis,structure and photoluminescent properties

A 3d–4f heterometallic coordination polymer, {[EuCu(C₂O₄)(na)₂] ·?2H₂O} _n (1) [Hna=nicotinic acid], has been synthesized by hydrothermal reaction of lanthanide oxides, Cu(I), and pyridine-2,3-dicarboxylic acid. 1 features a 3-D pillar-layered coordination framework constructed from two-dimensional lanthanide-carboxylate layers and Cu(na) pillars. Interestingly, the na ligand was obtained by the in situ decarboxylation of pyridine-2,3-dicarboxylic acid.     

Synthesis,Crystal Structures,and Photoluminescence of Lanthanide Coordination Polymers with 4‐Acetamidobenzoate

The reactions of Ln(NO₃)₃ · 6H₂O and 4‐acetamidobenzoic acid (Haba) with 4,4′‐bipyridine (4,4′‐bpy) in ethanol solution resulted in three new lanthanide coordination polymers, namely {[Ln(aba)₃(H₂O)₂] · 0.5(4,4′‐bpy) · 2H₂O}_∞ [Ln = Sm ( 1 ), Gd ( 2 ), and Er ( 3 ), aba = 4‐acetamidobenzoate]. Compounds 1 – 3 are isomorphous and have one‐dimensional chains bridged by four aba anions. 4,4′‐Bipyridine molecules don’t take part in the coordination with Ln^III ions and occur in the lattice as guest molecules. Moreover, the adjacent 1D chains in the complex are further linked through numerous N–H ··· O and O–H ··· O hydrogen bonds to form a 3D supramolecular network. In addition, complex 1 in the solid state shows characteristic emission in the visible region at room temperature.     

A novel three‐dimensional heterometallic coordination polymer: poly[[diaquadi‐μ3‐chlorido‐μ2‐chlorido‐tri‐μ3‐nicotinato‐tricopper(I)gadolinium(III)] hemihydrate]

In the title polymeric heterometallic compound, {[Cu₃Gd(C₆H₄NO₂)₃Cl₃(H₂O)₂]·0.5H₂O}_n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the Gd^III centers display a bicapped trigonal prismatic geometry, defined by six carboxylate O atoms and two water molecules. For copper(I), one Cu center is three‐coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four‐coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ₂‐ and μ₃‐bridging modes, linking the Cu^I ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxylate O atoms linking to two Gd^III ions and the N atom linking to one Cu^I ion. Thus, a novel three‐dimensional heterometallic coordination polymer is constructed from Gd–carboxylate subunits and Cu—Cl chains. In addition, intra‐ and intermolecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three‐dimensional structure. Topologically, the framework represents an unusual 3,6‐connected (4.8²)₃(4¹⁰.6⁵) net.     

Stable Heterometallic CuII‐BaII‐2,5‐Thiophenedicarboxylate Framework with High Capacity for Light Hydrocarbons

The heterometallic Cu^II‐Ba^II coordination polymer, namely [CuBa(tdc)₂(H₂O)(DMF)]_n ( 1 ) (H₂tdc = 2,5‐thiophenedicarboxylic acid, DMF = N,N′‐dimethylformamide), was solvothermally synthesized by the reaction of H₂tdc, CuCl₂ · 2H₂O, and Ba(NO₃)₂. Single crystal X‐ray diffraction analysis reveals that compound 1 features a 3D intricate framework with the 1D channels occupied by the coordinated solvent molecules. After removing the coordinated solvent molecules, the desolvated samples of 1a exhibit high capacity for light hydrocarbons.     

Synthesis and crystal structure of heteronuclear La( III )‐Cu(II ) complex { [LaCu2(NTA)2(4,4′‐bpy)(H2O)3]NO3·5H2O}n

A novel La( III )‐Cu( II ) heterometallic coordination polymer {[LaCu₂(NTA)₂(4,4′‐bpy)(H₂O)₃]NO₃·5H₂O]_n, where H₃NTA denotes nitrilotriacetic acid and 4,4′‐bpy denotes 4, 4‐bipyridine, was synthesized and characterized by IR spectrum, elemental analysis and X‐ray diffraction. The complex crystallizes in the triclinic space group Pi with cell parameters a = 1.33710(10) nm, b = 1,44530(10) nm, c =1.0949(2) nm, α = 71.905(7)°, β = 74.327(7)°, γ = 64.427(9)°, V = 1.7912(4) nm³and Z = 2. It consists of heterometallic units, in which each La( II ) ion is coordinated in a distorted monocapped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA^3? ions, and each Cu( I ) ion is coordinated by one nitrogen atom from 4,4′‐bpy and one nitrogen atom, three oxygen atoms from NTA^3?. In the title complex, La( I ) ions and Cu( II ) ions are connected by the heterometallic bridging of NTA^3?, constructing a two‐dimensional network structure along the [110]. And it is extended into an infinite three‐dimensional network structure by the formation of homometallic bridging of Cu‐4, 4′‐bpy‐Cu, exhibiting a certain inclusion ability.