Syntheses,Crystal Structures,and Magnetic Properties of Two Cobalt Coordination Polymers Constructed From 1,3‐Bis(2,4‐dicarboxyphenyl) Benzene and Bis(imidazole) Linkers

Abstract. The 3D cobalt(II) coordination polymers [Co_1.5(HDDB)(1,4‐bib)_1.5(H₂O)]_n ( 1 ), and {[Co₂(DDB)(1,3‐bib)₂(μ₂‐H₂O)] · H₂O}_n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H₄DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (6³)₄(6⁵ · 8⁸ · 10²) net, and complex 2 is an unprecedented dinuclear [Co₂(COO)(μ₂‐H₂O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(3² · 4³ · 5⁴ · 6³ · 7 · 8²) net. Additionally, the magnetic properties of 2 were investigated.     

Zinc(II) and Cadmium(II) Metal Complexes with Bis(tetrazole) Ligands: Synthesis and Crystal Structures

Two new metal complexes [Zn( L¹ )]_n ( 1 ) and [Cd₃( L² )₂Cl₂(H2O)6]_n ( 2 ) (H₂ L¹ = 1,5‐bis(tetrazol‐5‐yl)‐3‐oxapentane, H₂ L² = bis(tetrazol‐5‐yl)methane) have been synthesized and characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction analysis. Complex 1 was a 2‐D sheet constructed by L¹ and Zn(II) center, further assembled to form a three‐dimensional (3‐D) supramolecular networks through weak hydrogen‐bonding interactions. In the complex 2 , there were two unequivalent Cd(II) centers, and some of ligands L² adopted chelate coordination mode, and others adopted bridge coordination mode linking the Cd1 center and simultaneously bridging the Cd2 center, the Cl^‐ anions adopted μ₂ bridging mode, ligands L² and the Cl^‐ anions linked the Cd(II) centers to form a 3‐D supramolecular networks.     

钴、镍-氨基三乙酸配位聚合物Na[M(nta)]·H2O(M=Co,Ni)的水热合成、结构与磁性

由有机配体同金属离子作用构建的配位聚合物具有与无机微孔晶体类似的空旷骨架结构,并在非线性光学材料、磁性材料、超导材料及催化等诸多方面具有潜在的应用前景[1～4].在配位聚合物的合成中,配体的种类不仅直接影响到聚合物的合成,而且还涉及到聚合物的结构维数[5～7].目前,用来构建这些配合物的有机配体大多数都带有相同的可配位基团,较少应用具有两种以上的配位基团的有机配体.本文采用同时含有氮和氧两种配位原子的多齿配体氨基三乙酸[8～12],在水热条件下分别以Co2+和Ni2+作为组装基元,通过自组装合成了具有三维骨架结构的Na[M(nta)]·H2O [M=Co(1),Ni(2)]配位聚合物,并进行了结构与磁性研究.     

Copper(I) and Silver(I) Coordination Polymers Based on Rigid Bis(triazole) Ligand: Syntheses,Structures, and Catalytic Properties

Two metal coordination polymers, [Cu₂(btb)(CN)₂]_n ( 1 ) and [Ag₂(btb)(muco)]_n ( 2 ) [btb = 4, 4′‐bis(1, 2,4‐triazolyl‐1‐yl)‐biphenyl, H₂muco = trans,trans‐muconic acid], were synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, and X‐ray single‐crystal diffraction. Complex 1 exhibits a 1D ladder‐chain structure containing cyanide anions, which are generated in situ by the cleavage of C–C bond of acetonitrile molecules under solvothermal conditions, whereas 2 possesses a rare 3D framework with binodal 4, 6‐connected fsh topology. In addition, the thermal behavior, fluorescence and catalytic properties of the complexes for the degradation of methyl orange in a Fenton‐like process were investigated.     

Syntheses,Crystal Structures,and Optical and Magnetic Properties of Some CsLnCoQ3 Compounds (Ln = Tm and Yb,Q = S; Ln = Ho and Yb,Q = Se)

The four new compounds CsTmCoS₃, CsYbCoS₃, CsHoCoSe₃, and CsYbCoSe₃ have been synthesized at 1123 K. These black‐colored isostructural compounds crystallize in the KZrCuS₃ structure type with four formula units in space group Cmcm of the orthorhombic system. The structure of these compounds is composed of layers separated by Cs atoms. Because there are no Q–Q bonds, the formal oxidation states of Cs/Ln/Co/Q are 1+/3+/2+/2?, respectively. CsHoCoSe₃ shows paramagnetic behavior with μ_eff = 11.9(1) μ_B, whereas CsYbCoS₃ displays an antiferromagnetic‐like transition at ～2.7 K with μ_eff = 5.85(1) μ_B. Both CsYbCoS₃ and CsYbCoSe₃ exhibit optical band gaps in the near infrared region and broad absorption bands at lower energies.     

吡啶二亚胺Ni(Ⅱ)配合物的合成、晶体结构及其催化乙烯聚合的研究

由三齿配体2,6-二[1-(2-甲基苯基亚胺)乙基]吡啶(L₁)和2,6-二[(1-苯基亚胺)乙基]吡啶(L₂)分别与NiCl₂.6H₂O在乙腈中反应,合成了两个吡啶二亚胺基氯化镍配合物L₁Ni(Ⅱ)Cl₂.CH₃CN(1)和L₂Ni(Ⅱ)Cl₂(2).通过元素分析、IR和¹HNMR对配体和配合物进行了结构表征,并测定了配合物1和2的晶体结构.X射线衍射分析结果表明,两个配合物均为五配位扭曲三角双锥构型,属单斜晶系,C_c空间群.配合物1的晶胞参数a=2.5783(5)nm,b=1.4843(3)nm,c=1.5866(3)nm;β=122.82(3),°V=5.1024(18)nm³,Z=4,R₁=0.0708,配合物2的晶胞参数a=1.5772(1)nm,b=0.8594(1)nm,c=1.5459(1)nm;β=103.27(1),°V=2.039(2)nm³,Z=4,R₁=0.0375.配合物1和2经MAO活化后对乙烯聚合表现出较低的催化活性.     

Syntheses,Crystal Structures,and Magnetic Properties of Carboxylate-Bridged Copper(II) Complexes with Bis(2-Pyridylmethyl)Amino Acids

Tetradentate Schiff-base carboxylate-containing ligands, bis(2-pyridylmethyl)amino-5-valeric acid (Hpmva) and bis(2-pyridylmethyl)amino-6-caproic acid (Hpmca), react with copper(II) perchlorate to give rise to the carboxylated bridged chain complexes {[Cu(μ-pmva)(H₂O)](ClO₄)}_n (1) and {[Cu(μ-pmca)(H₂O)](ClO₄)}_n (2). These complexes have been characterized by X-ray crystallography, spectroscopic, and variable-temperature magnetic susceptibility measurements. In 1 and 2, each of the copper(II) ions exhibit CuN₃O₂ coordination environments with the three nitrogen atoms of the ligand and one oxygen atom belonging to the carboxylate group of an adjacent molecule occupying the basal position and a water molecule coordinated in the axial position. The electronic spectra of the complexes are significantly affected by the coordination geometry. Magnetic susceptibility measurements indicate that complexes exhibit very weak ferromagnetic interactions.     

Tetrachloroferrate(III) Complexes Containing Some Heteroaromatic Organic Cations: Structures and Magnetic Properties

The crystal structures of tetrachloroferrate(III) complexes having stoichiometry (BH)⁺ [FeCl₄]^? (where B = isoquinoline and 4‐aminopyridine) were determined at 100 K. While weak interactions, particularly N–H···Cl hydrogen bonds, are evident in the structures, distances between the Fe(III) centers are quite long in both cases. The structure of the compound with B = quinoline was compared with that previously established at room temperature, and showed that neither solid‐solid nor magnetic phase transitions occurred in this temperature range. Magnetic measurements on the paramagnetic powders indicate weak antiferromagnetic interactions transmitted through the crystal lattice, giving rise to Néel temperatures that are significantly below 10 K. Comparisons are made with other characterized [FeCl₄]^? compounds having similar organic base cations, enabling clarification of the superexchange mechanism.     

Syntheses,Crystal Structures,and Properties of Metal(II) Coordination Polymers based on Flexible Ligand 1,3‐Bis(4‐phenoxy)benzenedicarboxylic Acid and Bis(benzimidazole)

Three new coordination polymers, [Zn(PBDC)(bbbm)_0.5]_n ( 1 ), [Co(PBDC)(bbbm)]_n ( 2 ), and [Cd(PBDC)(bbbm)]_n ( 3 ) were prepared via hydrothermal reactions of different metal(II) nitrates with flexible 1,3‐bis(4‐phenoxy)benzenedicarboxylic acid (H₂L) and 1,1‐(1,4‐butanediyl)bis(benzimidazole) ligand. All these complexes were fully characterized by elemental analysis, FT‐IR, thermogravimetric analysis (TGA), powder X‐ray diffraction, and single‐crystal X‐ray diffraction. Structure analyses revealed that complex 1 has a 2D→2D twofold interpenetrating framework simplified by a 4‐connected sql net with point symbol (4⁴.6²), whereas complexes 2 and 3 are isostructural and exhibit a 2D→2D twofold interpenetrating framework rationalized as a three‐connected hcb net with point symbol (6³). Complexes 1 – 3 further expand to 3D supramolecular structures through non‐covalent C–H ··· O interactions. Additionally, the luminescent and magnetic properties of some of these complexes were studied. Complex 3 presents ideal photoluminescent behavior, whereas complex 2 shows antiferromagnetic coupling between the central Co^II ions, suggesting its latent application in magnetic material.     

Cobalt(II)‐Terephthalate Frameworks Containing Bis(benz­imidazole) Derivative Co‐ligands: Syntheses,Crystal Structures,Catalytic and Fluorescence Properties

Two metal‐organic coordination polymers of Co^II with the molecular formulae [Co(L₁)(tp)(H₂O)₂]_n ( 1 ) and [Co(L₂)(tp) · H₂O]_n ( 2 ) [L₁ = 1, 4‐bis(benzimidazole‐1‐ylmethyl)‐ benzene; L₂ = 1, 1‐(1, 4‐butanediyl)bis(5, 6‐dimethylbenzimidazole); tp = terephthalate] were synthesized and characterized by single‐crystal X‐ray diffraction studies, infrared spectroscopy (IR), thermogravimetric analysis (TGA), X‐ray powder diffraction (XRPD), and elemental analysis. The structure determination of complex 1 reveals a 2D layer with (4, 4) topology, with Co^II ions at the nodes connected through tp and L₁ co‐ligands. Complex 2 is the first example of a four‐connected SrAl₂ structure type ( sra , 4²6³8 topology) with threefold interpenetration in Co^II coordination frameworks, forming by bridging L₂ and tp co‐ligands. In addition, the fluorescence and catalytic performances of the complexes for the degradation of methyl orange were investigated.     

Hydrothermal Synthesis,Crystal Structures,and Catalytic Properties of Three Coordination Polymers Containing ­Flexible Bis(benzimidazole) and Dicarboxylate Ligands

Three metal‐organic coordination polymers, namely {[Cd(L1)(1,2‐chdc)] · 2H₂O}_n ( 1 ), {[Ni(L2)(1,2‐chdc)] · H₂O}_n ( 2 ), and [Cd(L2)(npht)]_n ( 3 ) [L1 = 1,2‐bis(2‐methylbenzimidazol‐1‐ylmethyl)benzene, L2 = 1,2‐bis(5,6‐dimethylbenzimidazol‐1‐ylmethyl)benzene, 1,2‐H₂chdc = 1,2‐cyclohexanedicarboxylic acid, H₂npht = 3‐nitrophthalic acid] were synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction methods, IR spectroscopy, TGA, and elemental analysis. In compound 1 , two 1,2‐chdc^2– ligands connect two neighboring Cd atoms to form a dinuclear [Cd₂(1,2‐chdc)₂] subunit, which is further linked by L1 ligands to construct a 1D ladder‐like chain. Compound 2 exhibits a 2D (4,4) coordination network with {4⁴.6²} topology, whilst compound 3 shows a 1D helical chain structure. The fluorescence, UV/Vis diffuse reflection spectra, and catalytic properties of complexes 1 – 3 for the degradation of the congo red azo dye in a Fenton‐like process are investigated.     

Kristallstruktur-Untersuchungen von Bis(pentafluorphenyl)tellurdihalogeniden (C6F5)2TeHal2 (Hal = Cl,Br)

Crystal Structure Determinations of Bis(pentafluorophenyl)tellurium Dihalides (C₆F₅)₂TeHal₂ (Hal = Cl, Br) Bis(pentafluorophenyl)telluriumdichloride and bis(pentafluorophenyl)telluriumdibromide crystallize at 10°C or 20°C from CH₂Cl₂ or CHCl₃ solution in the monoclinic space group P2₁/c with a = 649.5(1) pm, b = 1 275.6(2) pm, c = 1 816.2(5) pm, β = 92.89(2)° for (C₆F₅)₂TeCl₂ and a = 694.4(1) pm, b = 1 579.1(2) pm, c = 1 423.4(1) pm, β = 90.22(2)° for (C₆F₅)₂TeBr₂ with four formula units per each unit cell.     

Synthesis,Crystal Structures,and Magnetic Properties of Two Copper(II) Radical Heterospin Complexes

Two heterospin complexes [Cu(NIT3Py)(cda)H₂O] · H₂O ( 1 ) and [Cu(NIT2Py)(cda)H₂O] · H₂O · CH₃OH ( 2 ) with Cu^II ions and pyridyl‐substituted nitronyl nitroxide radicals (NITxPy = 2‐(x′‐pyridyl)‐4,4,5,5‐tetramethyl‐imidazoline‐1‐oxyl‐3‐oxide, x = 3, 2; H₂cda = 4‐hydroxy‐pyridine‐2,6‐dicarboxylic acid) were synthesized and characterized structurally and magnetically. The single crystal structures show that the two complexes are both two‐spin complexes, in which the different radicals make the two complexes have different hydrogen bonding interactions to form 2D and 1D supramolecular network for complexes 1 and 2 , respectively. The magnetic measurements indicate that complexes 1 and 2 both exhibit antiferromagnetic interactions between Cu^II and radicals.     

A Novel Ruthenium(III) and Lithium Complex: Synthesis,Crystal Structure,and Magnetic Properties

A novel complex [Li₃{μ‐(H₂O)₆}(H₂O)₆]·[RuCl₆] has been synthesized and was characterized by single‐crystal X‐ray diffraction. The compound crystallizes in rhombohedral space group R3¯c, with the unit cell parameters a = b = 9.948(2)Å, c = 33.376(14)Å, γ = 120°, V = 2860.5(15)ų, Z = 6, D_c = 1.918 Mg m^—3, μ = 1.703 mm^—1, R = 0.0244, wR = 0.0478. The compound consists of a cation, which contains three lithium ions linked by six bridged water molecules, and an anion, which contains a ruthenium(III) ion. The whole complex can be described as a three‐dimensional structure linked by hydrogen bonds between cation and anion. The magnetic properties of the complex have been investigated. The IR, UV‐vis and EPR spectra are studied.     

Modular Construction,Structures, and Magnetic Properties of Two Manganese Coordination Polymers Based on 3,5‐Bis(2–carboxylphenoxy)benzoic Acid

Two manganese(II) coordination polymers, namely, [Mn_1.5(BCB)(bpy)_1.5(H₂O)]_n ( 1 ), and [Mn(HBCB)(bibp)₂(H₂O)] ( 2 ), were assembled from the mixed ligands of the flexible tripodal ligand of 3,5‐bis(2‐carboxylphenoxy)benzoic acid (H₃BCB) and two rigid N‐donors [bpy = 4,4′‐bipyridine, and bibp = 4,4′‐bis(imidazolyl)biphenyl]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectra, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Structural analysis reveals that complex 1 is a 3D (3,4,6)‐connected {5 · 6²}₂{5⁶ · 6⁴ · 7 · 8² · 9²}{6⁴ · 8 · 9} net based on two kinds of inorganic nodes of dinuclear {Mn₂(COO)₂} SBUs and Mn(2) ions. Complex 2 is a hydrogen bonds based 3D supramolecule with 6‐connected {4¹² · 6³}‐ pcu net. Besides, the variable‐temperature susceptibilities of 1 and 2 were investigated.     

New Binuclear Copper Complexes [(9S3)Cu(CN)Cu(9S3)]Xn (X=BF4, n=1; X=TCNQ,n=2) (9S3=1, 4, 7‐trithiacyclononane): Syntheses,Crystal Structures and Magnetic Properties

The binuclear Cu complex salts of 1, 4, 7‐trithiacyclononane (9S3) with an inorganic anion (BF₄)^‐ and with an organic radical anion TCNQ^‐ (7, 7′, 8, 8′‐tetracyanoquinodimethanide) were synthesized and their molecular and crystal structures were examined in connection with the magnetic properties. The new complex cation [Cu(9S3)CN(9S3)Cu]⁺ varies its charges and magnetic properties depending on the counter anions; [Cu(9S3)CN(9S3)Cu](BF₄) ( 1 ) was obtained as diamagnetic colorless crystals, while [Cu(9S3)CN(9S3)Cu](TCNQ)₂ ( 2 ) was obtained as dark blue crystals with antiferromagnetic properties. Complex 1 crystallized in the monoclinic space group C2/c with a = 26.863(2), b = 7.0878(5), c = 13.4864(8) Å, β = 116.318(2)°. Complex 2 crystallized in the triclinic space group P1¯ with a = 12.521(1), b = 20.2698(8), c = 8.0205(4) Å, α = 100.688(4), β = 93.846(5), γ = 94.953(4)°. Both complexes are comprised of cyano‐bridged two Cu(9S3) ions with tetrahedral coordination. The X‐ray structural study revealed that 1 has two crystallographically equivalent copper(I) atoms, while 2 has two crystallographically independent Cu^I/II sites. The two Cu^I/II sites could not be distinguished from the X‐ray structural study. For 2 the IR spectra show that both crystallographically independent TCNQ species were monoanions and are strongly dimerized due to π‐stacking, which well explains their diamagnetic contribution to the magnetic susceptibility and the highly insulating property of this salt. The temperature‐dependent magnetic susceptibility of 2 showed a deviation from the Curie‐Weiss behaviour around 60 K, which indicates a strong antiferromagnetic intermolecular interaction between the copper complexes and that such intermolecular interaction should partly occur via the TCNQ radical anion dimer.     

Synthesis, crystal structure and magnetic behavior of two cobalt coordination polymers with 1,2-bis(1,2,4-triazol-1-yl)ethane and dicyanamide

Two cobalt(II) coordination polymers formed from bte (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), namely [Co(bte)₂(dca)₂]_n (1) and {[Co(bte)(dca)₂] · H₂O}_n (2), have been synthesized and characterized by elementary analyses, IR, thermogravimetric analyses, X-ray diffraction analyses and magnetic measurements. Compound 1 is a double-chain with Co(II) centers bridged by bte, containing metallocycles of [Co₂(bte)₂] and trans dca as termination ligands. In 2, each Co(II) center is bonded by two bridging bte ligands and four dca as μ-1,5-dca in different orientations in the 3D network.     

席夫碱类三明治型铽/镝金属配合物的合成、表征及磁性

以N,N′-二(4-甲氧基水杨基)邻苯二胺(H2L)为配体合成了2个新的稀土配合物[M_2L_3(H_2O)](M=Tb (1),Dy (2)),并对它们进行了红外分析、元素分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为三明治型双核配合物。此外还研究了配合物1和2的磁学性质,结果表明配合物1和2都表现出反铁磁性作用和场诱导效应引起的慢弛豫行为。配合物2的有效能垒和驰豫时间分别为35.45 cm-1和2.7×10~(-10) s。     

Syntheses,structures, and luminescent properties of Zn(II) and Cd(II) complexes: 3-D supramolecules based on 2,6-bis(imino)pyridine ligands constructed by hydrogen bonding interactions

Six 5-coordinate 2,6-bis(imino)pyridine metal complexes, [2,6-(ArN=CMe)₂C₅H₃NMCl₂ · nCH₃CN] (Ar = 4-MeC₆H₄, M = Zn, n = 0.5, Zn1, M = Cd, n = 1, Cd1; Ar = 2,6-Et₂C₆H₃, M = Zn, n = 0.5, Zn2, M = Cd, n = 0.5, Cd2; Ar = 2,4,6-Me₃C₆H₂, M = Zn, n = 1, Zn3, M = Cd, n = 1, Cd3), were synthesized in acetonitrile by the reactions of the corresponding bis(imino)pyridines with ZnCl₂ or CdCl₂ · 2.5H₂O, respectively. The structures of Zn1–Zn3 and Cd1–Cd3 were determined by the single-crystal X-ray diffraction. In all complexes, the ligand is tridentate with further coordination by two chlorides, resulting in a distorted trigonal bipyramid. All complexes self-assemble through hydrogen bonding interactions to form a 3-D supramolecular structure. At 298 K in dichloromethane, all complexes have blue luminescent emissions at 405–465 nm, which can be attributed to ligand-centered π* → π transitions. The zinc and cadmium centers play a key role in enhancing fluorescent emission of the ligands.     

Crystal Structures,Magnetic Properties and Catecholase‐Like Activities of μ‐Alkoxo‐μ‐Carboxylato Double Bridged Dinuclear and Tetranuclear Copper(II) Complexes

One μ‐alkoxo‐μ‐carboxylato bridged dinuclear copper(II) complex, [Cu₂(L¹)(μ‐C₆H₅CO₂)] ( 1 )(H₃L¹ = 1,3‐bis(salicylideneamino)‐2‐propanol)), and two μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear copper(II) complexes, [Cu₄(L¹)₂(μ‐C₈H₁₀O₄)(DMF)₂]·H₂O ( 2 ) and [Cu₄(L²)₂(μ‐C₅H₆O₄]·2H₂O·2CH₃CN ( 3 ) (H₃L² = 1,3‐bis(5‐bromo‐salicylideneamino)‐2‐propanol)) have been prepared and characterized. The single crystal X‐ray analysis shows that the structure of complex 1 is dimeric with two adjacent copper(II) atoms bridged by μ‐alkoxo‐μ‐carboxylato ligands where the Cu···Cu distances and Cu‐O(alkoxo)‐Cu angles are 3.5 11 Å and 132.8°, respectively. Complexes 2 and 3 consist of a μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear Cu(II) complex with mean Cu‐Cu distances and Cu‐O‐Cu angles of 3.092 Å and 104.2° for 2 and 3.486 Å and 129.9° for 3 , respectively. Magnetic measurements reveal that 1 is strong antiferromagnetically coupled with 2J =‐210 cm^?1 while 2 and 3 exhibit ferromagnetic coupling with 2J = 126 cm^?1 and 82 cm^?1 (averaged), respectively. The 2J values of 1–3 are correlated to dihedral angles and the Cu‐O‐Cu angles. Dependence of the pH at 25 °C on the reaction rate of oxidation of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to the corresponding quinone (3,5‐DTBQ) catalyzed by 1–3 was studied. Complexes 1–3 exhibit catecholase‐like active at above pH 8 and 25 °C for oxidation of 3,5‐di‐tert‐butylcatechol.