Hydrothermal synthesis and crystal structure of two new lanthanide coordination polymers with 1,2-phenylenediacetate

Two new compounds {[Ln₂(1,2-pda)₃(H₂O)₂]·?2H₂O} _n (1,2-H₂pda?=?1,2-phenylenediacetic acid, Ln?=?Tb, 1; Ho, 2) were prepared by hydrothermal reaction and characterized by X-ray crystallography. The Ln³⁺ is nine-coordinate by eight oxygen atoms of six 1,2-pda ligands and one oxygen of water. Ln³⁺ ions are bridged by 1,2-pda ligands via bridging/chelating-bridging pentadentate and chelating-bridging/chelating-bridging hexadentate coordination to form 3-D framework structures. Complex 1 emits strong green fluorescence corresponding to ⁵D₄???⁷F_j (j?=?6–3) transitions of the Tb³⁺.     

Yttrium-succinates coordination polymers: Hydrothermal synthesis, crystal structure and thermal decomposition

New polymeric yttrium-succinates, Y₂(C₄H₄O₄)₃(H₂O)₄·6H₂O and Y₂(C₄H₄O₄)₃(H₂O)₂, have been synthesized, and their structures (solved by single crystal XRD) are compared with that of Y₂(C₄H₄O₄)₃(H₂O)₂·H₂O. Three compounds were obtained as single phases, and their thermal behaviour is described.     

Hydrothermal synthesis, crystal structure and properties of 2-D and 3-D lanthanide sulfates

Two new lanthanum sulfates DySO₄(OH) 1 and Eu₂(SO₄)₃(H₂O)₈2 have been hydrothermally synthesized. The colorless crystals were characterized by IR, TGA, ICP and XRD. The structure was determined by single-crystal X-ray diffraction. 1 crystallizes with monoclinic symmetry, space group P2(1)/n [a=7.995(4) Å, b=10.945(5) Å, c=8.164(4) Å, α=90°, β=93.619(6)°, γ=90°, V=713.0(5) Å³, Z=8]. It displays a three-dimensional framework, based on the novel Dy-O chains connected by the sulfate groups through helical chains. 2 crystallizes with monoclinic symmetry, space group C2/c, [a=13.5605(17) Å, b=6.7676(8) Å, c=18.318(2) Å, α=90°, β=102.265(2)°, γ=90°, V=1642.7 (4) Å³, Z=4]. Its layered framework is attained by the europium atoms connected by the sulfate groups arranged in a helical manner.     

Hydrothermal synthesis and structural characterization of three lanthanide coordination polymers with adipic acid and 1,10-phenanthroline

Three new lanthanide coordination polymers, [Ln(Ad)_3/2(Phen)] _n ·2nH₂O (Ln = Eu, 1; Pr, 2; Ad = adipate; Phen = 1,10-phenanthroline) and [Yb(Ad)_3/2(Phen)] _n ·nH₂O 3, were prepared by hydrothermal reactions. The structures of 1, 2 and 3 are reported. In compound 1, Eu(III) ions are bridged by adipate ligands in two modes into 2-D polymeric layers. Adjacent layers are assembled by hydrogen bonding and π–π stacking between 1,10-phenanthrolines into a 3-D supramolecular structure. Compound 2 is isostructural with 1. In compound 3, the Yb(III) ions are connected by adipate ligands in three modes into a 3-D network.     

Two novel 3-D bismuth oxalates with organic amines protruding in channels

Two novel 3-D oxalate-containing bismuth compounds of formula (C₃N₂H₅)₂ [Bi₂(C₂O₄)₄(H₂O)₂]·2H₂O 1 and [NH(C₂H₅)₃][Bi₃(C₂O₄)₅] 2 were obtained by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic P2/n space group with , , , β=97.280(3)°, Z=4, R₁=0.0340 and wR₂=0.0766 for unique 4734 reflections I>2σ(I). Compound 2 belongs to the orthorhombic Pbcn space group with , , , Z=4, R₁=0.0222 and wR₂=0.0568 for unique 2472 reflections I>2σ(I). The Bi^III centers have nine-fold coordination for 1 and eight-fold for 2 with the Bi atoms in distorted monocapped square antiprism and distorted dodecahedron, respectively. And oxalate ligands adopt different coordination modes: bidentate for 1, bidentate and tricoordinate for 2. Compounds 1 and 2 are both 3-D open-framework structures containing channels with guest molecules. These two compounds exhibit intense blue luminescence with the emission peaks at 419 nm for 1 and 442 nm for 2, respectively, in the solid state at room temperature. These compounds with novel structural frameworks could be useful in the field of photoactive materials.     

Hydrothermal synthesis of two layered indium oxalates with 12-membered apertures

Two layered indium oxalates, In(C₂O₄)_2.5(C₃N₂H₁₂)(H₂O)₃, I, and In(C₂O₄)_1.5(H₂O)₃, II, have been hydrothermally synthesized. In I, the linkage between indium and oxalate units gives rise to a sheet with a rectangular 12-membered aperture (six indium atoms and six oxalate units). Indium atom of II has an unusual pentagonal bipyramidal coordination arrangement. The connectivity between indium and oxalate units forms a neutral puckered layer with 12- (along a-axis) and eight-membered (along b-axis) apertures. Crystal data for these two indium oxalates are as follows: I, triclinic, space group: P-1 (No. 2), a=8.725(3) Å, b=9.170(3) Å, c=9.901(3) Å, α=98.101(4)°, β=97.068(4)°, γ=102.403(4)°, V=756.3(4) Å³, Z=2, M=463.0(5), ρ_calc=2.042 g/cm³, R₁=0.0377, wR₂=0.0834. II, monoclinic, space group: P2₁/c (No. 14), a=10.203(5) Å, b=6.638(1) Å, c=11.152(7) Å, β=95.649(4)°, V=751.7(4)ų, Z=4, M=300.9(0), ρ_calc=2.659 g/cm³, R₁=0.0229, wR₂=0.0488. TG analyses indicate the water molecules of I can be removed at 150°C. The dehydrated product retains structural integrity.     

水热法合成Bi2S3纳米管及其生长机理

以硝酸铋[Bi(NO)3]和硫化钠(Na2S)为反应原料, 采用水热法在120 ℃下反应12 h, 制备出Bi2S3纳米管. 利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、选区电子衍射(SAED)和高分辨透射电镜(HRTEM)对其结构和形貌进行了表征. 结果表明, 所制备的产物是结晶良好的正交相Bi2S3纳米管, 其外径为100~500 nm, 内径为50~200 nm, 长为1~5 μm. 根据实验结果讨论了Bi2S3纳米管的生长机理. 初步研究了反应温度和矿化剂种类对产物形貌和结构的影响.     

Synthesis, structure, and fluorescence of two cadmium(II)-citrate coordination polymers with different coordination architectures

Two novel Cd(II)-citrate complexes were obtained with different metal/ligand ratios through hydrothermal method. Their structures were determined by single-crystal X-ray diffraction analysis. Although their topological structures are both 2-D layer network assemblies, both central Cd(II) ions and Hcit³⁻ ligands display completely different coordination modes. In polymeric complex 1, Hcit³⁻ serves as a μ₁₀-bridged and central Cd(II) ions adopt 6- and 8-coordinated configurations. In contrast, a μ₉-bridged and 6- and 7-coordinated environments between Cd(II) and Hcit³⁻ are established in the polymeric complex 2. Two Complexes remain stable up to approximately 300 °C. The complex 1 exhibits strong fluorescent emission band at 450 nm (λ=346 nm) as well as complex 2 exhibits strong fluorescent emission band at 430 (λ=346 nm).     

Hydrothermal synthesis,characterization and photoluminescence property of a novel indium phosphate with 3D supramolecular structure

A one-dimensional chained indium phosphate In(H₂PO₄)(HPO₄)(C₁₀N₂H₈) (1) was synthesized under hydrothermal condition using 2,2′-bipyridine as a ligand and characterized by IR spectroscopy, ICP and elemental analyses, powder and single crystal X-ray diffraction analyses. Compound 1 crystallizes in the triclinic system, space group P-1. The connection of In-centered octahedra (InO₄N₂) and P-centered tetrahedra ({PO₃(OH)} and {PO₂(OH)₂}) constructs a new type of 1D chained structure with In/P ratio of 1/3. Interestingly, H₂PO₄ tetrahedron and 2,2′-bipyridine ligands "hanging" in the chain by bridging oxygen atoms and nitrogen atoms bond to the central In atoms. It is noted that the adjacent chains are stably packed together and the final structure exhibits interesting three-dimensional (3D) supramolecular array via π–π interactions of the 2,2′-bipyridine groups and hydrogen-bond interactions. Additionally, compound 1 shows strong photoluminescence property in the solid state at room temperature.     

Hydrothermal synthesis,crystal structure,and electrochemical property of a new 3-D coordination polymer based on benzene-1,2,4,5-tetracarboxylate bridging ligand: [Cu2(btec)(en)2] n

A new 3-D copper(II) complex, formulated as [Cu₂(btec)(en)₂] _n (1) [H₄btec = benzene-1,2,4,5-tetracarboxylate, and en = ethylenediamine], was hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single crystal X-ray diffraction. The structural analysis of 1 reveals that copper(II) connect by μ₆-bridging btec to form a 3-D coordination polymer, in which four carboxylates of btec show monodentate and bidentate coordination. Complex 1 was used as solid bulkmodifier to fabricate renewable carbon paste electrode (1-CPE) by direct mixing method. The cyclic voltammogram of 1-CPE displayed one-electron quasi-reversible redox waves in potential range 300 to ?300 mV due to Cu(II)/Cu(I). Moreover, 1-CPE showed electrocatalytic activity toward the reduction of nitrite.     

Design,synthesis and structure of uranyl coordination polymers from 2-D layer to 3-D network structure

Solvothermal reaction of uranyl acetate and succinic acid in DMF resulted in formation of three uranyl coordination polymers, [(UO₂)₄(μ₂-OH)₇(OH)₆]·2(H₂O)·(H₃O)·4NH₂(CH₃)₂ (1), [(UO₂)(μ₂-OH)(OH)₃]·2NH₂(CH₃)₂] (2), and [(DMF)₂(UO₂)(μ₂-OH)₄(UO₂))] (3). The products were characterized by elemental analysis, IR spectroscopy, X-ray single crystal, and powder diffraction. Structural analysis shows that 1 is a layer, 2 and 3 are 3-D network structures.     

Solvothermal synthesis and crystal structure of a 3-D hexagonal metal-porphyrin coordination network

A hexagonal-shaped hybrid metal-porphyrin framework containing 5,15-di(4-pyridyl)-10,20-diphenylporphyrin (trans-H₂DPyP) and Zn(NO₃)₂6H₂O in DMF has been self-assembled solvothermally. The solvothermal reaction of Zn(II) with conformationally versatile 5,15-di(4-pyridyl)-10,20-diphenylporphyrin, which can coordinate axially to two ligands, resulted in metalation of the porphyrin core and then self-coordination of the metalated porphyrin-produced single crystals of 3-D polymeric arrays. The trans-ZnDPyP framework is thermally stable at 450?°C and allows solvent exchange without losing the crystal structure.     

Hydrothermal synthesis and crystal structure of a new two-dimensional zinc citrate complex

A new two-dimensional compound C₁₂H₁₄O₁₆Zn₃ (1), containing seven-coordinate zinc atoms was prepared by the hydrothermal technique. The compound obtained was characterized by TG-DTA, single crystal X-ray diffraction, elemental analysis and FT-IR analysis. Single-crystal X-ray diffraction analysis shows that compound 1 crystallizes with monoclinic symmetry in the space group P2₁/c, a?=?6.1552(13)?Å, b?=?14.546(3)?Å, c?=?9.581?Å, β?=?102.66(2)°, V?=?836.9(4)?ų, Z?=?2, R1?=?0.0311, wR2?=?0.0830.     

Hydrothermal synthesis and structural characterization of two unprecedented photoluminescent coordination polymers constructed from Cd salt and mixed ligand

Two new Cd-containing coordination polymers {Cd₂(succ)₂(1,10′-phen)₂} _n (1) and {Cd(glut)(1,10′-phen)(H₂O)} _n (2) are described. Complex 1 exhibits an interesting 2-D structure in which the binuclear Cd centers are linked by succinate anions. Complex 2 possesses an interesting 1-D chain-like structure. The IR and TG properties of the two compounds are studied. Furthermore, these two complexes exhibit photoluminescence.     

First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H₂O)]_n[Ln = Eu (1), Ho (2); H₂APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal–organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H₂APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents – in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.     

Two second-order non-linear optical coordination polymers with noninterpenetrating honeycomb-like 2-D (6,3)-type networks

Two isostructural metal–organic frameworks, [ML(H₂O)₄]_n (M = Y(II) (1) and Nd(II) (2)), NaH₂L = 5-sulfoisophthalic monosodium salt), have been synthesized by hydrothermal reactions. Each metal is nine-coordinate with a distorted tricapped trigonal prismatic arrangement. L^3? is a μ³ bridge to generate a homometallic 2-D noninterpenetrating (6,3) honeycomb-like topological network structure. The luminescence spectra indicate emission maxima at 406 and 402 nm, respectively. Compounds 1 and 2 show second-harmonic generation responses that are 0.5 and 0.8 times that of urea, respectively.     

具有生物活性的1,4-二氢吡啶衍生物的水热法合成及结构表征

1,4-二氢吡啶衍生物具有很好的生理活性。在医学上用作心血管疾病的防治保健药物,不仅能治疗肠胃疾病、雷诺氏病、脂肪肝、中毒性肝炎,也有抗衰老、防早熟等作用,还可以用作治疗肺动脉高压和癫痫病的辅助药物[1-2]。近年又发现1,4-二氢吡啶衍生物不但是一类高效的钙拮抗剂,亦是一种绿色饲料添加剂。它的合成通常采用文献报道的Hantzsch法合成[3],即将干燥氨气通入乙酰乙酸乙酯与醛的混合溶液中。该反应时间长、操作复杂,且氨气易对环境造成污染。正因为此,越来越多的化学家和药物学家将有机合成的研究重点放在对环境无污染的绿色合成上。如…     

Hydrothermal synthesis,structure, and properties of lead(II)-based coordination compounds with R-isophthalic acid (R=OH,CH3)

Three new lead(II)-based coordination polymers, [Pb(5-OH-BDC)] _n ?·?nH₂O (1) (5-OH-BDC?=?5-hydroxyisophthalate), [Pb₂(5-CH₃-BDC)₂] _n (2), and [Pb₂(5-CH₃-BDC)₂(phen)₂] _n ?·?2nH₂O (3) (5-CH₃-BDC?=?5-methylisophthalate, phen?=?1,10-phenanthroline), have been hydrothermally synthesized, structurally determined by single-crystal X-ray diffraction, and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Both 1 and 2 exhibit 2-D double-layer network structures, while 3 possesses 1-D chain structure bridged by 5-CH₃-BDC. The coordination sphere of Pb(II) in 1 is holodirected, whereas in 2 and 3 the spheres feature hemidirected structures. Fluorescence properties of 1–3 have been investigated in the crystalline state at room temperature.     

Hydrothermal synthesis of two perovskite rare-earth manganites, HoMnO3 and DyMnO3

Two perovskite rare-earth manganites RMnO₃ (R=Ho, Dy) were synthesized from the hydrothermal redox reactions of KMnO₄ and MnCl₂ at 250 °C and characterized by means of X-ray diffraction, scanning electron microscopy and SQUID. They are orthorhombic, whereas the hexagonal phases, which were competitive strongly with the orthorhombic phases in solid-state reactions, are avoided in the hydrothermal systems. The pure metastable manganites may serve as a model for understanding the magnetisms of Jahn-Teller distortion and charge ordering. This new synthetic approach leaves many rooms for new doped or undoped RMnO₃ compounds.