Two Cd(II) coordination polymers based on asymmetrical Schiff-base ligand with five- and six-membered N-containing heterocyclic rings: Synthesis,crystal structures and luminescent properties

Two cadmium inorganic–organic hybrid coordination polymers [CdL(SCN)₂]_n (1) and [CdLI₂]_n (2), have been synthesized and characterized by IR spectroscopy, elemental analysis, XRPD, thermogravimetric (TG) analyses and X-ray crystallography, where L is 4-(pyridine-4-yl)methyleneamino-1,2,4-triazole. Asymmetrical Schiff-base ligand L acts as a bidentate bridging ligand to bind two Cd(II) centers through two terminal N_triazolyl and N_pyridyl donors in polymers 1 and 2. Polymer 1 displays a new 3D inorganic–organic hybrid network generated through the coordination interactions between Cd-(1,3-μ-SCN⁻) 2D inorganic sheets and bidentate bridging ligands. The structure of polymer 2 is a 3D chiral supramolecular framework which contains helical chains on 2₁ axis. Each Cd(II) center is coordinated by two ligands and two I⁻ donors to attain a distorted tetrahedral environment. The luminescent properties of polymers 1 and 2 were investigated in the solid state at room temperature.     

Synthesis,X-ray structure and luminescent properties of a new 1D terbium(III) coordination polymer based on 2,4-dichlorophenoxyacetate and 4,4′-bipyridine

A new 1D terbium coordination polymer, {[Tb(2,4-dcpa)₃(H₂O)₂]·(4,4′-bpy)_1.5(H₂O)₂}_n (1) [2,4,-dcpa = 2,4-dichlorophenoxyacetate, 4,4′-bpy = 4,4′-bipyridine], was prepared by hydrothermal synthesis and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Complex 1 exhibits an infinite chain structure with a {Tb₂(2,4-dcpa)₆(H₂O)₄} dimeric repeat unit. Each Tb³⁺ ion is nine-coordinated to two water molecules, one monodentate carboxylate group and four bridging carboxylate groups in which the carboxylate groups are bonded to the terbium ion in one modes: the chelating–bridging tridentate. Three-dimensional fluorescence spectra of 1 were detected at room temperature under the excitation and the emission wavelengths in the range of 420–750 nm with the interval of 5 nm. The lifetime of 1 in solid-state at room temperature up to 1.132 ms. On the other hand, poor luminescence efficiency has been noted for the Tb³⁺-2,4-dcpa complex.     

Synthesis,structure and luminescent properties of two-dimensional lanthanum(III) porous coordination polymer based on pyridine-2,6-dicarboxylic acid

The novel porous coordination polymer {[La₄(PDA)₁₀(H₂O)₈]·2H₂O}_n with two-dimensional framework has been prepared by hydrothermal synthesis of pyridine-2,6-dicarboxylic acid (H₂PDA) and lanthanum nitrate under mild conditions and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P-1. La(III) ions in the coordination polymer are nine-coordinated and have N₁O₈ or N₂O₇ polyhedral units connected to the PDA^2? anions forming tricapped trigonal prism geometries. The H₂PDA ligands coordinate to the central La(III) ions in bridging tetradentate and pentadentate modes. The thermal decomposition of the complex has been predicted with the help of thermal analyses (TG and DTG). The complex exhibits luminescent property in the near-UV at room temperature in the solution of DMSO due to the π^* → n or π^* → π transitions of PDA^2? anions.     

The crystal structure of R10Co9In20 (R=Er, Tm, Lu) compounds

New ternary indides R₁₀Co₉In₂₀ (R=Er, Tm, Lu) have been found in the systems {Er, Tm, Lu}–Co–In at 870 K. The crystal structure of Tm₁₀Co₉In₂₀ has been refined using single-crystal X-ray data: Ho₁₀Ni₉In₂₀ structure type, P4/nmm space group, Z=2, a=13.166(5) Å, c=9.097(4) Å, V=1577(2) ų, R=0.0315 for 335 unique reflections hkl (DARTCH-1 diffractometer, MoK_α radiation). The coordination polyhedra of the Tm atoms have 16 and 17 vertices, those of the In atoms 12 and 13 vertices and those of the Co atoms 8 and 10 vertices. The structure can be described as a stacking of polyhedra formed by In atoms.     

Synthesis,structure and luminescent properties of neodymium(III) coordination polymers with 2,3-pyrazinedicarboxylic acid

The coordination polymer [Nd₂(pzdc)₃(H₂O)]_n·nH₂O (complex I) with three-dimensional framework has been prepared by hydrothermal synthesis of 2,3-pyrazinedicarboxylic acid (pzdc) and neodymium nitrate and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group P2(1)/c. Every Nd(III) atom in the coordination polymer is nine-coordinated with different coordination environments. The pzdc ligands coordinate to the central Nd(III) atoms in bridging tetradentate, hexadentate, or heptadentate modes. The thermal decomposition of the complex has been predicted with the help of thermal analyses (TG, DTG and DTA). Complex I exhibits luminescent emissions bands in the solid state at room temperature. The isomorphous complex [Nd₄(pzdc)₆(H₂O)₂]_n·3nH₂O (complex II) has also been prepared by hydrothermal reaction under different conditions. Luminescent emission of complex I display selectivity for some heavy metal ions.     

Lanthanide(III) halides: Thermodynamic properties and their correlation with crystal structure

Temperatures and enthalpies of phase transitions of 17 lanthanide(III) halides determined experimentally are reported. Correlations were made between temperature of fusion of lanthanide(III) halides, on the one hand, and enthalpy of fusion, on the other, versus atomic number of lanthanide. According to this classification, the lanthanide(III) halides split into groups, as also do the corresponding crystal structures. A correlation between the crystal structure of lanthanide(III) halides and their respective entropy of fusion (or entropy of fusion + entropy of solid–solid phase transition) was inferred from the aforementioned features. Fusion in those halides with hexagonal, UCl₃-type and orthorhombic, PuBr₃-type, structures entails an entropy of fusion change (or entropy of fusion + entropy of solid–solid phase transition change) by 50 ± 4 J mol⁻¹ K⁻¹. The homologous entropy change within the group of halides having the rhomboedric, FeCl₃-type, structure, is smaller and equals 40 ± 4 J mol⁻¹ K⁻¹. Halides with monoclinic, AlCl₃-type, crystal structure constitute a third group associated to an even smaller entropy change upon fusion, only 31 ± 4 J mol⁻¹ K⁻¹. The halides with lower entropies of fusion also have a lower S_1300 K − S_298 K indicating either a higher degree of order in the liquid or a higher entropy in the solid at room temperatures.     

A new conducting polymer of 2,5-bis(2-thienyl)-1H-(pyrrole) (SNS) containing carbazole subunit: Electrochemical, optical and electrochromic properties

We report here the synthesis of a new electroactive monomer 3,6-di-tert-butyl-[4-(2,5-di-2-thienyl-1H-pyrrol-1-yl)phenyl]-9H-carbazole in five steps and polymerization of this monomer by two different procceses: Kumada Coupling and electro-oxidative. The product obtained by chemical polymerization exhibits a high thermal stability and narrow molecular weight distribution. While, in the UV–vis absorption spectrum of monomer the absorption peaks appear at 338 nm, the chemically synthesized polymer absorbs at 428 nm with 90 nm red shift. Cyclic voltammogram of monomer shows two separate oxidation processes which reflect the first oxidation at +0.84 V and a second one at +1.43 V. When the polymeric film prepared by electrochemical process was subjected to a repeated cyclic scan between −0.2 V and +1.0 V, it switches among three different colors (orange, green and blue). The oxidation and reduction response times were calculated as 2.0 s for this polymer film and exhibits high redox stability. The results anticipate that this kind of polymers can be used for designing electrochromics based on the use of one molecule for the generation of three basic colors (RGB).     

配合物Cu（phen）（m-CBA）2的合成、晶体结构及磁性（英文）

采用间氯苯甲酸(m-CBA)、1,10-菲罗啉(phen)和醋酸铜合成一种新颖配合物Cu(phen)(m-CBA)2,并用红外光谱、紫外可见光谱、元素分析、X-射线单晶衍射对其进行表征。结果表明,该配合物为单斜晶系,空间群为C2/c,晶胞参数为a=2.9699(4)nm,b=1.15452(2)nm,c=1.5335(2)nm,β=111.118(2)°,V=4.9051(1)nm3,Z=8,F(000)=2328,R1=0.0728,wR2=0.2234[I>2σ(I)]。结果分析表明,中心铜原子和来自1个1,10-菲罗啉分子的2个氮原子、2个间氯苯甲酸分子的2个氧原子进行配位,形成一个变形平面四边形的配位模式。该配合物中铜原子之间存在顺磁相互作用。     

三（2,2,6,6-四甲基-3,5-庚二酮）酸钌（III）的合成及性质

以三氯化钌和2,2,6,6-四甲基-3,5-庚二酮为原料,在甲醇中合成了β-二酮前驱体-三(2,2,6,6-四甲基-3,5-庚二酮)酸钌(III)。通过元素分析、红外光谱、核磁共振谱、紫外-可见光谱等对其进行了表征,确定了配合物的结构组成。采用 TG-DTA 分析了配合物在空气和氮气中的热分解行为,为MOCVD 镀钌和钌的氧化物薄膜工艺提供热力学数据与参考。     

Synthesis, crystal structure and properties of two ternary rare earth complexes with aromatic acid and 1,10-phenanthroline

Two dimeric rare-earth complexes [Eu(o-MOBA)₃phen]₂·2H₂O (1), [Tb(o-MOBA)₃phen]₂·2H₂O (2), (where o-MOBA = o-methoxybenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. Both of them consist of neutral dimeric molecules, crystallize in triclinic system, space group P. Each RE(III) ion is nine-coordinated with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, two bidentate bridging carboxylate groups and two tridentate bridging carboxylate groups. Complex 1 shows bright red luminescence, 2 shows green luminescence under UV light at room temperature, respectively. The thermal analysis indicates that they are all quite stable to heat.     

羧酸铑(II)轴向配合物的合成、表征及催化性能

以羧酸铑(II)为母体,吡啶-2-基(吡啶-4-基)甲酮(24ma)为轴向配体,合成了4种新型羧酸铑(Ⅱ)轴向配合物,且成功培养出化合物单晶。使用1H NMR、13C NMR、MS、IR和X-单晶射线衍射对其结构进行表征,讨论了取代基和轴向配体对分子结构的影响,并初步测试了它们对美罗培南类化合物合成反应的催化性能。结果表明,与母体分子羧酸铑(II)相比,所选定的羧酸铑(Ⅱ)轴向配合物因在反应体系中溶解度较差、配体不易解离等原因,导致催化合成美罗培南类化合物的产率不高。     

Synthesis,electrochemical, and spectroelectrochemical properties of conductive poly-[2,5-di-(2-thienyl)-1H-pyrrole-1-(p-benzoic acid)]

Poly(ter-heteroaromatic(thiophene-pyrrole-thiophene)), PDPB, was electrochemically prepared from the 2,5-di(2-thienyl)-1H-pyrrole-1-(p-benzoic acid) (DPB) monomer using the Paal-Knorr pyrrole condensation reaction. The structure of the monomer was confirmed using ¹H-, ¹³C NMR, FT-IR and mass spectroscopy. The maximum UV–visible absorption and PL emission bands of DPB were observed at 330 nm and 500 nm, respectively. The cyclic voltammograms (CVs) recorded for the electrochemically polymerized DPB revealed a set of redox peaks at 0.65/0.53 V. The conductivity monotonically increased with respect to the applied potential from 0.0 V to 1.0 V, exhibiting a maximum conductivity of 0.18 S/cm at +0.80 V. The in situ UV–visible spectroelectrochemical analysis of PDPB revealed electronic transitions at 420 nm, 654 nm, and 870 nm corresponding to the π–π* transition, polaron, and bipolaron states, respectively. The optical band-gap (E_g) of PDPB was 2.16 eV. The color of the PDPB film transitioned yellow (at 0.0 V) to blue (at 1.0 V) when the potential was switched between the reduced and oxidized states with a good electrochromic response time (0.95 s).     

四(亚硝基)合钯酸钾的合成、单晶结构及其循环伏安特征

以醋酸钯(PdAc2)与亚硝酸钾(KNO2)为起始原料,水为溶剂,合成四亚硝基钯酸钾(K2[Pd(NO2)4]),产率为96.5%。采用溶剂挥发法培养出其单晶,经X射线单晶衍射分析证实:此晶体由中心对称的[Pd(NO2)4]^2-配阴离子,K⁺阳离子和2分子结晶水组成,为三斜晶系,P-1空间群,晶胞参数为:a=6.4953(5) nm,b=7.0134(5) nm,c=7.1473(5) nm,α=118.784(2)°,β=101.050(2)°,γ=98.085(2)°,Z=1,Pd-N键长为2.014 nm和2.037 nm,∠N-Pd-N为91.70(4)°,且Pd²⁺位于4个N原子组成的平面四边形的中心。采用恒电位仪在室温下测试其循环伏安图,测得其还原峰电位(Ep)为-0.51 V (vs. SCE)。     

顺式-碘氯[(1R,2R)-(-)-1,2-环己二胺]合铂(Ⅱ)的合成及结构表征

为了合成新型铂抗癌药物米铂的代谢产物之一顺式-碘氯[(1R,2R)-(-)-1,2-环己二胺]合铂(Ⅱ),以K2PtCl4为起始原料先后与二甲基亚砜、(1R,2R)-(-)-1,2-环己二胺、AgNO3、KI和KCl反应合成目标化合物。采用元素分析、质谱、核磁共振氢谱、红外光谱和热分析方法分析其组成和结构,结果显示合成的化合物结构与标题化合物一致。     

Synthesis,structure and luminescent properties of 3D lanthanide (La(III), Ce(III)) coordination polymers possessing 1D nanosized cavities based on pyridine-2,6-dicarboxylic acid

Two novel coordination polymers, namely, {[Ln₂(PDA)(HPDA) (H₂O)₄ClSO₄]·2H₂O}_n (Ln = La(III) and Ce(III) for complexes I and II, respectively) were synthesized through the reaction between pyridine-2,6-dicarboxylic acid (H₂PDA) and La(NO₃)₃·6H₂O and Ce₂(SO₄)₃·8H₂O under hydrothermal conditions. Both of these polymers possess 1D infinite nanosized cavities embedding guest water molecules. The complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. Two compounds crystallize in orthorhombic system, space group Pna2(1). Both of the complexes exhibit 3D metal–organic framework structure, where SO₄^2? anions play as the bridge between 1D wavelike chains and the adjacent parallel pyridine rings were arranged through π–π interactions. The bi-bidentate coordination mode of SO₄^2? anion was observed. Luminescent emissions of complex I were measured in the solution of DMF at room temperature. In addition, the luminescent emissions of complex I showed certain selectivity among some metal ions.     

Crystal growth and structure of La3MGa5O14 (M=Ti, Zr, Hf)

La₃M⁴⁺Ga₅O₁₄ (M=Ti, Zr, Hf) compounds were crystallized using the micro-pulling down and Czochralski techniques. Both growth methods showed that these three crystals are peritectic compounds. The structure of La₃TiGa₅O₁₄ (LTiG) crystal was refined using single-crystal X-ray diffraction data. LTiG was observed to be isostructural to Ca₃Ga₂Ge₄O₁₄ (P321 (No.150), Z=1) and the lattice parameters are a=8.223(1), c=5.109(1) Å. The Ti atoms were found to occupy octahedral (1a) and tetrahedral (3f) sites coordinated by six and four oxygen atoms, respectively.     

((R)-(-)-1,2-丙二胺)(1,3-丙二酸)合铂(II)的合成、表征及抗肿瘤活性研究

以1,2-丙二胺为起始原料,经手性拆分得到R-(-)-1,2-丙二胺,再同氯亚铂酸钾、碘化钾、硝酸银、1,3-丙二酸钠等物质反应,制成((R)-(-)-1,2-丙二胺)(1,3-丙二酸)合铂(II),通过元素分析、红外光谱、核磁共振等对其进行化恘结构确证,结果表明所合成产品同理论一致,并进行初步体外活性评价,表明该化合物对于肺癌A-549及白血病HL-60肿瘤细胞有一定活性。     

Synthesis,crystal structure and anticancer activity of 2D-coordination polymer of cerium(III) with chiral Schiff base trans-N,N′-bis-(2-hydroxy-1-naphthalidehydene)-(1R,2R)-cyclohexanediamine

The chiral Schiff base coordination polymer [Ce(H₂L)₃(NO₃)₃Ce(H₂L)₃(NO₃)₃(H₂O)]_n [H₂L: trans-N,N′-bis-(2-hydroxy-1-naphthalidehy-dene)-(1R,2R)-cyclohexanediamine] was synthesized and characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. X-ray crystallography shows that the Ce(III) coordinates with three neutral Schiff base ligands and three nitrates. One Ce(III) is nine-coordinated by three oxygen atoms from three different Schiff base ligands and six oxygen atoms from three nitrates, the other Ce(III) is ten-coordinated because of the coordination of an additional water molecule. Each Schiff base ligand serves as a bridging ligand to link Ce(III) ions through oxygen atoms, leading to a coordination polymer. The Ce(III) coordination polymer displays two dimensional plane grid network structure. The antiproliferation activities of the ligand H₂L and its Ce(III) coordination polymer on MDA-MB-231 breast cancer cells were also studied by MTT (3-[4,5-dimethyltiazol-2-yl]-2,5-diphenyl-tetrazolium bromide) method. The results indicate that H₂L and [Ce(H₂L)₃(NO₃)₃Ce(H₂L)₃(NO₃)₃(H₂O)]_n can inhibit the cellularproliferation. Moreover, the coordination polymer had higher antiproliferative activity than that of the ligand.     

Synthesis, crystal structure and X-ray excited luminescent properties of LuBa3B9O18

A new compound LuBa₃B₉O₁₈ has been prepared by a high-temperature solid-state reaction and its crystal structure was determined by powder X-ray diffraction methods. The results of Rietveld refinement show that it is isotypic to YBa₃B₉O₁₈. The X-ray excited luminescent properties of LuBa₃B₉O₁₈ were investigated. It shows a broad emission band in the wavelength range of 300–550 nm with peak center at 385 nm. Its room temperature fluorescent decay profile exhibits a single-exponent shape with decay time of 15 ns. It is believed that the lattice defects have played an important role on the luminescent performances of LuBa₃B₉O₁₈ powders and its thermal luminescence measurement confirmed the existence of lattice defects in it. Considering the emission wavelength, luminescence intensity, decay time, melting point, density and non-hygroscopic property of LuBa₃B₉O₁₈, one has reason to assume that it might find an application as a new scintillation material.