A New 4-Connected Co(II) Coordination Framework With an Uncommon Two-Fold Interpenetrating Net: Synthesis, Structure and Luminescence Property

The coordination polymer [Co(pbc)₂(H₂O)]_n(Hpbc = 3-Pyrid-4-ylbenzoic acid) was prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, FTIR spectra and element analysis. X-ray diffraction analysis reveals that the pbc⁻ ligands act as diconnectors to link two Co(II) centers and adopt a two coordination mode: μ ₂-N, O and μ ₂-N, O, O to form infinite wavy cobalt-carboxylate chains along the bc plane. Furthermore, compound, [Co(pbc)₂(H₂O)]_n, shows intense photoluminescence at room temperature.     

A novel luminescent 3D metal–organic framework possessing 4-fold interpenetrating (3,4)-connected net

A novel 3D polymer [Zn(L¹)(1,4-BDC)_0.5] (1) (HL¹ = 3,5-bis(pyridin-4-ylmethoxy)benzoic acid, 1,4-BDC = 1,4-benzenedicarboxylate anion) has been isolated under hydrothermal condition and characterized by single crystal X-ray diffraction. Compound 1 displays a 3D 4-fold interpenetrating (3,4)-connected net with (4 · 8²)(4 · 8⁵) topology. In addition, powder X-ray diffraction, photoluminescent property and thermogravimetric analysis for 1 are investigated in detail.     

A 3D 3d-4f Heterometallic Coordination Polymer: Synthesis,Crystal Structure and Properties

Abstract  A three-dimensional heterometallic coordination polymer formulated as Sm₂Zn₂(BIPA)₅(H₂O)₂ (1) (H₂BIPA = 5-bromoisophthalic acid) was synthesized by hydrothermal reaction of H₂BIPA with Sm₂O₃ and Zn(NO₃)₂. Complex 1 shows an 8-connected (3⁶.4¹⁸.5³.6) topological network. The thermal analysis of complex 1 has been measured and discussed. Additionally, the photoluminescent property of complex 1 was investigated. Graphical Abstract  An intriguing feature of complex 1 is a 3D eight-connected framework of 3⁶.4¹⁸.5³.6 topology.      

三维锌孔道配位聚合物的合成及结构

在DMF/H2O/C2H5OH混合体系中,以2-(4-吡啶)-咪唑二羧酸为有机连接体与Zn2+反应得到了一个新的含有孔道的三维锌配位聚合物,分子式为:Zn3(HL)3(DMF)2.2DMF,H3L=2-(4’-吡啶)-咪唑二甲酸,DMF=N,N-二甲基甲酰胺。单晶X射线分析显示1是带有一维矩形孔道的三维开骨架结构,孔道直径大小为18.28×6.952。     

Development and Demonstration of Americium (III)-Europium (III) Separation Using Diglycolamic Acid

The extraction behavior of Eu(III) and Am(III) in a solution of bis(2-ethylhexyl)diglycolamic acid (HDEHDGA) in n-dodecane (n-DD) from citric acid (CA) medium was studied as a function of various parameters. The extraction increased with increase of pH, reached a maximum at pH 2 followed by decrease. The stripping behavior of Eu(III) and Am(III) from the loaded organic phase was studied by using a solution of diethylenetriaminepentaacetic acid (DTPA) and CA. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized. Based on the optimized conditions, the feasibility of separating Am(III) from Eu(III) present in CA feed solution was investigated in a 20- stage mixer-settler. Quantitative extraction of Eu(III) and Am(III) in 0.1 M HDEHDGA/n-DD was achieved in 3–4 stages, whereas the selective back extraction of Am(III) was achieved in ～20 stages upon contacting the loaded organic phase with a stripping formulation composed of DTPA-CA at pH 1.5. The results confirmed the possibility of using diglycolamic acid for the separation of trivalent actinides from the chemically similar lanthanides, which is indeed necessary for transmutation of minor actinides present in high-level liquid waste (HLLW).     

Novel Diglycolamic Acid Functionalized Iron Oxide Particles for the Mutual Separation of Eu(III) and Am(III)

Iron oxide (Fe₃O₄) particles functionalized with diglycolamic acid (Fe-DGAH) were synthesized and characterized by TG-DTA, X-Ray diffraction,¹H NMR, and scanning electron microscopy (SEM). The extraction behavior of Am(III) and Eu(III) in Fe-DGAH was studied from dilute nitric acid medium to examine the feasibility for the mutual separation of trivalent actinides and lanthanides using Fe-DGAH. For this purpose, the effect of various parameters such as the duration of equilibration and concentrations of europium, nitric acid, and diethylenetriaminepentaacetic acid (DTPA) in the aqueous phase on the distribution ratio (K_d) of Am(III) and Eu(III) was studied. The conditions needed for the efficient separation of Am(III) from Eu(III) were optimized using DTPA. The distribution ratio of ?10⁴ mL/g was obtained for both Am(III) and Eu(III) at pH 3, and it decreased with an increase in the concentration of nitric acid. However, a separation factor of Eu(III) over Am(III) of ?150 was achieved in the presence of DTPA. Rapid sorption of metal ions in the initial stages of equilibration followed by the establishment of equilibrium occurred within 2 h. The sorption data were fitted to the Langmuir adsorption model, and the apparent europium sorption capacity was determined to be ?50 mg/g. The study indicated the feasibility of using Fe-DGAH particles for magnetic separation of Eu(III) from Am(III) with high separation factors.     

A 3D Gd–Ag coordination polymer constructed from pyridine-3,5-dicarboxylic acid: Synthesis, crystal structure and magnetic properties

A novel heterometallic coordination polymer, [AgGd(PDC)₂]·2H₂O (1) (H₂PDC = pyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features an unusual three-dimensional network structure in which infinite gadolinium-carboxylate chains are linked by [Ag(PDC)₂]³⁻ metalloligands to form a mixed-metal coordination network. Moreover, the luminescent properties and magnetic properties of 1 have also been investigated.     

[Co(COOH)_2·2H_2O]的合成及晶体结构

利用溶剂热法合成了新型甲酸钴配位聚合物[Co(COOH)_2·2H_2O]。采用单晶X射线、粉末X射线(XRD)、元素分析、红外光谱(IR)、热重分析(TGA)表征了该配合物的结构。结果表明[Co(COOH)_2·2H_2O]晶体属单斜晶系,P_(21)c空间群,a=8.8334(11),b=7.2816(9),c=9.6103(12),α=90.00,β=97.666(2),γ=90.00,V=612.62-3,Z=4。     

An Infinite Sandwich-Type Copper (I) Coordination Polymer Containing 2-D Double Chains Layers Structure Intercalated with the Terephthalic Acid Layers

A high-quality single crystal structure of a new coordination polymer having the formula [Cu₂(μ-SO₄)(μ-bpy)₂ · (H₂ta)] _n (1) (H₂ta = terephthalic acid; bpy = 4,4′-bipyridine) was obtained when the in situ reaction of CuSO₄ · 5H₂O with H₂ta and bpy ligands under solvothermal conditions (H₂O/ethanol) were carried out. The results of the structural characterization show that Cu(I) ions are bridged by 4,4′-bipyridine to form infinite 1-D chains, which are further linked through the sulfate groups to form a 1-D double chain structure. The extensive hydrogen-bonding interactions between the sulfate anions and free terephthalic acid molecules have an important effect in generating the 2-D layer structures and finally an infinite 3-D sandwich-type coordination polymer. In addition, the luminescent properties of coordination polymer 1 are also discussed.     

One-Dimensional Cobalt(II) and Zinc(II) Succinato Coordination Polymers with Nicotinamide: Synthesis, Structural, Spectroscopic, Fluorescent and Thermal Properties

Cobalt(II) and zinc(II) succinato (suc) coordination polymers with nicotinamide (nia), {[Co(μ-suc)(H₂O)₂(nia)₂] · 2H₂O} _n (1) and {[Zn(μ-suc)(H₂O)₂(nia)₂] · 2H₂O} _n (2) have been synthesized and characterized by elemental analyses, magnetic moments, IR and TG-DTA. Single-crystal X-ray analyses of 1 and 2 reveal that these complexes are isostructural and crystallize in triclinic space group Complexes 1 and 2 are 1-D coordination polymers, in which the metal(II) ions exhibit an octahedral geometry with two suc, two nia and two aqua ligands. The nia ligand is N-bonded, while the suc ligand bridges the metal centers through the carboxylate groups. The 1D chains are further assembled to form 3D networks by strong N–H···O and OW–H···O hydrogen bonds. IR spectra confirm the coordination modes of both suc and nia ligands, while TG-DTA data are in agreement with the crystal structures. Fluorescent analysis in the solid state shows that all complexes display intraligand (π–π*) emissions of nia.     

A novel (3,4,8)-connected 3D topology framework based on [Gd2(bpdc)3(H2O)3] second building units

A new 3D coordination polymer {[Gd₂(bpdc)₃(H₂O)₃]·H₂O}_n(1) has been isolated from the reaction of 2,2′-bipyridine-4,4′-dicarboxylic acid (H₂bpdc) and Gd(III) salts under hydrothermal conditions. Single-crystal X-ray diffraction study shows that compound 1 is constructed from Gd₂-based second building units (SBUs) [Gd₂(bpdc)₃(H₂O)₃] and displays a 3D (3,4,8)-connected net with (4²·6)(3²·4²·5²)(3²·4⁵·5⁴·6¹¹·7⁶) topology. A thermogravimetric analysis of 1 shows a high thermal stability. The magnetic behavior of 1 reveals a weak antiferromagnetic interaction between Gd(III) ions.     

Removal of Arsenic(III), Chromium(III) and Iron(III) Traces from Hydrofluoric Acid Solutions by Specialty Anion Exchangers

The removal of As(III), Fe(III), and Cr(III) at trace levels from HF solutions by means of specialty ion exchange resins has been investigated. These impurities are usually found in technical‐grade HF, and they need to be removed to prepare metal‐free HF for the semiconductor industry. It was assumed that Fe(III) and As(III) species in dilute HF were present in anionic form, while Cr(III) was probably in neutral form, CrF₃. First, a selection of specialty ion exchangers was performed. Then, fixed‐bed experiments were carried out to check the ability of selected resins to reach the impurity levels required in SEMI C29 for 5 wt.% HF (5 ppb of As, and 10 ppb of Cr and Fe). The effect of the flow rate and the HF concentration on the metal removal was studied with Purolite D‐3777 and Fuji PEI‐CS‐07 resins respectively. Fuji PEI‐CS‐07 showed the best performance for Fe(III) removal, even at high HF concentration (25 wt.%). A strong decrease in the Cr(III) and As(III) removal capacity with increasing concentration of HF was observed.     

Synthesis, Characterization and Crystal Structure of a Novel One-Dimensional Supramolecular Dimethyltin (IV) Compound

A novel one-dimensional (1D) supramolecular dimethyltin compound of (Me₂SnO)₂(Me₂SnOCH₃)(O₂CCH₂SC₄H₃N₂-2,6)[Me₂Sn(O₂CCH₂SC₄H₃N₂-2,6)₂]·CH₃OH was prepared by the reaction of (CH₃)₂SnCl₂ with (2-pyrimidylthio)acetic acid with CH₃ONa as a base. The title compound contained four different tin atom environments. Among them, Sn(1) and Sn(2) were both five-coordinate with distorted trigonal bipyramidal geometries, Sn(3) was six-coordinate with a distorted octahedral geometry and Sn(4) was seven-coordinate with pentagonal bipyramidal geometry. Meanwhile, the compound was stabilized in a 1D infinite chain by intermolecular Sn–O bonds. An erratum to this article can be found at     

两个苯并咪唑羧酸稀土配合物的合成、晶体结构及荧光性质

合成了1,3-二羧甲基苯并咪唑有机配体,并与氯化铕、氯化钐反应得到了两个新的稀土配合物,通过元素分析、X-射线单晶衍射及X-射线粉末衍射对其进行表征。晶体结构表明,两个配合物结构均为两个金属中心被4个配体桥联形成Ln_2O_8型双核次级结构基元,通过(κ~1-κ~1-μ_2)-(κ~1)-μ_3配位模式与配体形成(4,4)拓扑的二维网络结构。同时测定了这两个配合物的热稳定性及Eu配合物的荧光性质。     

Syntheses and topological networks of two azide complexes based on 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole ligands

Two new azide complexes, [Cd₂(3-abpt)(N₃)₄]_n (1) and [Cu(3-abpt)₂(N₃)₂] (2) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), have been prepared and structurally characterized. Complex 1 displays an interesting 2D polymeric structure with rarely reported 3,7-connected (3²;4)(3⁴;4⁶;5⁶;6⁵) network in the Schafli notation. Complex 2 contains mononuclear pieces, and they are linked each other through weak CuN coordination bonds to form a 2D sheet with (4, 4) topology. The thermal stability and fluorescent property of 1 have also been investigated.     

Thermodynamic and Spectroscopic Studies on Am(III) and Eu(III) in the Extraction System of N,N,N',N'-Tetraoctyl-3-Oxapentane-1,5-Diamide in n-Dodecane/Nitric Acid

Abstract

Thermodynamic parameters (ΔG, ΔH, and ΔS) for the extraction of trivalent f-elements, M(III) (M = Am, Eu), with N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were determined in nitric acid/n-dodecane extraction system. The extraction of M(III) with TODGA was more exothermic than those with octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethyl phosphonate (DHDECMP). The difference in ΔH between the extractants was attributed to the difference in the binding mode between them, i.e. tridentate (TODGA) and bidentate (CMPO and DHDECMP). In addition, from the results of luminescence lifetime measurement, it was found that the inner-sphere of extracted Eu(III) was dehydrated completely, and occupied by TODGA and/or NO₃ ^?.     

三维网状配位聚合物[Mn5（suc）4（OH）2]n的合成与晶体结构

水热法合成了一种配位聚合物：[Mn5（suc）4（OH）2]n（H2SUC=丁二酸）,并通过元素分析、红外光谱进行了表征,用X-射线单晶衍射仪测定了配合物晶体结构。配合物属于单斜晶系,P21／C空间群,黠胞参数：a=9．572（2）,b=9．647（2）,c=12．526（3）A,V=1147．9（4）A3,Z=2,De=2．236g／cm^3,F（000）=766,μ（MoKa）=2．767mm^-1。对于2098个可观察到的衍射点（I〉2σ④（I））,R1=0.0292和WR2=0．0610。配合物是一个柱层式的兰维网状结构。