Hydrothermal syntheses and characterization of four 2-D lanthanide coordination polymers with glutarate and 1,10-phenanthroline

Four 2-D coordination polymers Ln₂(phen)₂(C₅H₆O₄)₃ [Ln?=?Pr(1), Eu(2), Er(3), Yb(4), phen?=?1,10-phenanthroline] were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data reveal that these complexes are isostructural. In the asymmetric unit, the two Ln(III) ions are nine-coordinate and have similar coordination environments. The Ln(III) ions are built into 2-D layers by three different coordination modes of glutarate. The resulting 2-D layer forms 3-D supramolecular architecture by two types of π···π stacking interactions. All the complexes were characterized by IR spectra and thermogravimetric analysis, and the emission spectrum shows that Eu₂(phen)₂(C₅H₆O₄)₃ possesses strong luminescence.     

Preparation of photoluminescent compounds of Eu(III), Sm(III), and Dy(III) containing anions of tetrafluoroterephthalic acid

The Ln₂(H₂O)₄(L)₃·2H₂O and Ln₂(phen)₂(L)₃·2H₂O complexes [Ln = Eu(III), Sm(III), or Dy(III); H₂L = C₆F₄(COOH)₂, phen = 1,10-phenanthroline] have been prepared. Structures of the prepared compounds have been confirmed by X-ray diffraction and IR spectroscopy studies. The complexes of Eu(III) have exhibited red photoluminescence stronger than that of the complexes of Sm(III) and Dy(III).     

3-((4，6-二甲基-2-嘧啶基)硫代)-丙酸和菲咯啉三元稀土配合物的晶体结构和发光性能

制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)₃(Phen)]₂·2H₂O(1)和[Tb(L)₃(Phen)]₂·2H₂O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。     

3-((4，6-二甲基-2-嘧啶基)硫代)-丙酸和菲咯啉三元稀土配合物的晶体结构和发光性能

制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)₃(Phen)]₂·2H₂O(1)和[Tb(L)₃(Phen)]₂·2H₂O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。     

The syntheses and magnetic properties of a series of heterospin [LnIIICuII 4] pentanuclear complexes

Twelve oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes Ln[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and PMoxd = the N,N′-Bi(α-pyridylmethyl)-oxamide dianion) and 12 oxamide-bridged Ln(III)–Cu(II) heteropentanuclear complexes with the formula of Ln[Cu(PEoxd)]₄(ClO₄)₃ · 5H₂O (PEoxd = the N,N′-Bi(α-pyridylethyl)-oxamide dianion) were synthesized and characterized. The magnetic properties of Gd[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (7) and Gd[Cu(PEoxd)]₄(ClO₄)₃ · 2H₂O (19) show that there are ferromagnetic interactions between Gd(III) and Cu(II) in the complexes with J _Cu–Gd = 1.38 cm^?1 and J _Cu–Gd = 1.00 cm^?1, respectively. Fluorescent quenching phenomena for Eu[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (6) and Tb[Cu(PMoxd)]₄(ClO₄)₃ · 5H₂O (8) were also observed.     

Two binuclear lanthanide complexes with 4-quinoline carboxylic acid: crystal structures and luminescent properties

Two isomorphic lanthanide complexes [Eu₂(L)₆(H₂O)₄] · 2H₂O (1) and [Tb₂(L)₆(H₂O)₄] · 2H₂O (2), (HL = 4-quinoline carboxylic acid) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Both complexes are binuclear and each metal center adopts nine-coordination with nine oxygens from two H₂O molecules and carboxylates of three ligands; L exhibits three different coordination modes. Luminescent properties of 1 and 2 at room temperature indicate that the triplet-state level of this ligand matches better with the lowest excited state level of Eu(III) than with Tb(III).     

Syntheses,crystal structures,and fluorescence properties of two isomorphic binuclear compounds incorporating N-acetyl-N-phenylglycinate with N-donor co-ligands

In this study, two new isomorphic binuclear compounds, [Ln(µ-NAP)₄(NAP)₂(phen)₂]?·?H₂O (1) and (2) (Ln?=?Eu, Tb, NAP?=?N-acetyl-N-phenylglycinate; phen?=?1,10-phenanthroline), have been synthesized and characterized by infrared spectroscopy, elemental analysis, and X-ray crystallography. These compounds crystallize in a triclinic form with space group Pī with a?=?11.7519(11), b?=?13.4293(12), c?=?14.0686(13)?Å, V?=?1992.7(3)?ų, and Z?=?1. Single-crystal X-ray structural analysis reveals that 1 is binuclear, assembled into a 3-D supramolecular network with self-complementary double hydrogen-bonding interactions and aromatic π–π interactions. Fluorescence properties of 1 and 2 are also discussed.     

Synthesis,structures and properties of ternary rare earth complexes with fluorobenzoic acid and 1,10-phenanthroline

Three dimeric rare-earth complexes [Eu(p-FBA)₃(phen)(H₂O)]₂ (1), [Tb(p-FBA)₃phen]₂ (2), and [Tb(o-FBA)₃phen]₂ (3) (where p-FBA = p-fluorobenzoate, o-FBA = o-fluorobenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. All are neutral dimeric molecules. Complex 1 crystallizes in triclinic system, space group P 1. Each Eu(III) ion is eight-coordinate with one 1,10-phenanthroline, one monodentate carboxylate, one water and four bridging carboxylates. Complex 2 crystallizes in triclinic system, space group P 1. Each Tb(III) is also eight-coordinate with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate and four bridging carboxylates. Complex 3 crystallizes in the monoclinic system, space group P2₁/c and consists of two crystallographically different binuclear molecules. Tb(III) ions are eight-coordinate with one 1,10-phenanthroline, one bidentate chelating carboxylate and four bridging carboxylates in both of them. Complex 1 shows bright red luminescence, 2 and 3 show green luminescence under UV light at room temperature. Thermal analysis indicates that are all quite stable to heat.     

Two 1-D europium coordination polymers: synthesis,crystal structure and fluorescence

Two new complexes {[Eu(2, 4-DFBA)₃ · (H₂O)₂] · H₂O} _n (1) and [Eu(2-BrBA)₃ · H₂O] _n (2) (2, 4-DFBA = 2, 4-difluorobenzoate, 2-BrBA = 2-bromobenzoate) have been synthesized and characterized by single crystal X-ray diffraction. 1 has a 1-D chain structure, in which Eu(III) ions are bridged by single COO^? groups and a 2-D supramolecular network is formed by hydrogen bond interactions. In 1, each Eu(III) is eight-coordinate with six oxygens from four 2,4-DFBA ligands and two waters. 2 has a 1-D chain structure, in which Eu(III) ions are bridged by bridging-chelating-bridging COO^? groups. In 2, each Eu(III) ion is nine-coordinate with eight oxygens from five 2-BrBA ligands and one water. The two complexes exhibit intense luminescence at room temperature. The ⁵D₀ → ⁷F _j (j = 0–4) transition emissions of Eu(III) have been observed.     

Hydrothermal synthesis and characterizations of a novel modular europium(III) coordination polymer bridged by biphenyl-2,2′-dicarboxylate dianions and 1,10-phenanthroline

A novel europium(III) coordination polymer, [Eu₂(bpdc)₃(phen)₂(H₂O)₂] _n ·nH₂O (1) (bpdc?= biphenyl-2,2′-dicarboxylate; phen?=?1,10-phenanthroline), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction methods. Complex 1 is monoclinic, space group C2/c, with a?=?24.3862(6), b?=?12.0792(3), c?=?22.9120(5)?Å, α?=?90.00, β?=?115.160(1), γ?=?90.00°, V?=?6108.8(3)?ų, Z?=?4, final R ₁?=?0.0605 and wR ₂?=?0.1760. Each Eu(III) ion is coordinated by six oxygen atoms from three carboxylate groups of three different bpdc anions, an oxygen atom from one coordinated water molecule and two nitrogen atoms from one phen ligand to complete a deformed monocapped square antiprism. Each pair of bpdc anions acts as a tetradentate ligand to connect two adjacent Eu(III) ions through chelating carboxylate groups, resulting in a centrosymmetric binuclear unit. Each binuclear unit links two adjacent binuclear units through two terminal bpdc anions to produce a one-directional zigzag chain. Two different kinds of hydrogen-bonding interactions link the chains and the lattice water molecules to form a hydrogen-bonding network.     

Reactions of heavier lanthanides with hydrazine in the presence of sulphur dioxide

Hydrazine hydrate reacts with sulphur dioxide in aqueous solution in the presence of heavier lanthanide(III) ions to give variety of complexes. The nature of product formed is highly pH dependent. Several hydrazine complexes of Ln(III) ions of the compositions Ln(N₂H₃SOO)₃(H₂O), Ln₂(SO₃)₃·2N₂H₄ and N₂H₅Ln(SO₃)₂(H₂O)₂ where Ln = Eu, Gd, Tb or Dy and the precursors for the hydrazinium lanthanide sulphite hydrates, the anhydrous lanthanide hydrazinecarboxylates, Ln(N₂H₃COO)₃ where Ln = Eu, Gd, Tb or Dy have been prepared and characterized by analytical, spectral, thermal and X-ray powder diffraction techniques. The infrared spectral data are in favour of the coordination of hydrazine and water molecules. These complexes decompose in three stages to yield respective oxides as final residue. The final residues were confirmed by their X-ray powder diffraction patterns and TG mass losses. The SEM photographs of some of the oxides show a lot of cracks indicating that large quantity of gases evolved during decomposition.     

双亲性希土-邻苯二甲酸正十四醇单酯-邻菲咯啉三元配合物的合成、表征、荧光特性及成膜性能

合成了双亲性的铕、铽-邻苯二甲酸正十四醇单酯-邻菲咯啉三元混配配合物，用红外光谱及差热-热重谱进行了表征。考察了发光性能。研究了它们在空气-水界面上的单分子膜行为，结果表明均具有良好的成膜行为。     

两个双核稀土-自由基化合物的合成、结构及磁性

以乙酰丙酮为共配体的稀土配合物与2-羟基苯取代的自由基配体进行反应得到2个新颖的稀土-自由基配合物[Ln₂（acac）₄（NIT-PhO）₂]（Ln=Tb（1）,Y（2）;acac=乙酰丙酮,NIT-PhOH=2-（2''-hydroxyphenyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide）。2个配合物的结构相同,均是通过2个自由基配体上的羟基氧原子桥联2个稀土离子构成双核结构。直流磁化率的研究表明配合物2具有弱的反铁磁性质。     

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.     

Three new binuclear copper(II) complexes with isonicotinic acid N-oxide: syntheses,crystal structures and properties

Three new copper(II) complexes with isonicotinic acid N-oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H₂O)]₂(NO₃)₂···2H₂O (1), [Cu(L)(phen)(H₂O)]₂(ClO₄)₂···2H₂O (2), and [Cu(L)(phen)Br]₂- [Cu(L)(phen)(H₂O)]₂Br₂···6H₂O (3) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu₂ dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N-oxide anion is bidentate, being coordinated to two Cu(II) ions through its N-O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie–Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes.     

CRYSTAL STRUCTURE OF THE ISOMORPHOUS COMPLEXES TETRAAQUABIS(2,6-DIHYDROXY-BENZOATO-O)(2,6-DIHYDROXY-BENZOATO-O,O)TERBIUM(III) AND HOLMIUM(III) DIHYDRATE

Abstract

The structures of isomorphic Tb(III) and Ho(III) complexes with 2,6-dihydroxybenzoic acid of formula [Tb(C₇H₅O₄] 2H₂O and [Ho(C₇H₅O₄)₃ 4H₂O] 2H₂O has been determined by X-ray diffraction and refined to a residual R = 0.030 for 5376 observed reflections and R = 0.0284 for 5660 observed reflections, for Tb(III) and Ho(III) complexes, respectively. Crystals are triclinic, space group P1 with a= 10.748(2), b=11.309(2), c = 12.452(2)Å, α = 82.28(3), ? = 73.05(5), γ = 68.27(3)° for Tb(III) and a= 10.731(2), b=11.269(2), c = 12.436(2)Å, α = 82.25(3), β = 72.92(3), γ = 68.46(3)° for Ho(III).

In the structure of these monomelic complexes the metal ions are coordinated by oxygen atoms of one bidentate chelating and two monodentate carboxylate groups and four molecules of water. Tb-O distances are in the range 2.323(3)-2.506(3) Å and Ho-0 2.297(3)-2.486(3) Å. The crystal structure, consisting of discrete units of neutral complexes with two molecules of water of crystallization is stabilized by intra-and intermolecular hydrogen bonds.     

Hydrothermal syntheses,structural characterization,and photoluminescent properties of five lanthanide coordination polymers

Five mixed-ligand coordination polymers, [Ln₂(PTCP)₂(m-BDC)₃] _n ?·?nH₂O (Ln?=?Pr (1), Sm (2), Eu (3), Tb (4), Dy (5); m-BDC?=?1,3-benzenedicarboxylate; PTCP?=?2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene), were synthesized and characterized by IR spectra, elemental analyses, thermogravimetric analyses, single-crystal X-ray diffraction, and solid-state photoluminescent spectra. X-ray crystallographic analyses reveal that the five complexes are 1-D structures based on dinuclear [Ln₂O₁₂N₄] units and further assembled into 3-D supramolecular networks by hydrogen bonds and π···π stacking interactions. The solids possess high thermal stabilities, with 3 and 4 exhibiting strong pure red and green characteristic emissions of Eu(III) and Tb(III) at room temperature.     

Synthesis,crystal structure,and luminescence properties of [TbGd(NAA)6(phen)2] and [Tb2(NNA)6(phen)2] · 2C3H7NO

Lanthanide(III) heteronuclear and binuclear complexes [TbGd(NAA)₆(phen)₂] (1) and [Tb₂(NAA)₆(phen)₂] · 2C₃H₇NO (2) (NAA = 1-naphthylacetic acid, phen = 1,10-phenanthroline) were prepared and their crystal structures were determined. In 1 and 2, each lanthanide is nine-coordinate by two bidentate-bridging and two tridentate chelating-bridging carboxylate groups, one bidentate chelating carboxylate and one phen molecule in a distorted monocapped square antiprism. The solid-state luminescence behavior and the antibacterial activities were studied. Complexes 1 and 2 exhibited characteristic emission of Tb(III) ion ⁵D₄ → ⁷F_J (J = 6–0) under UV radiation at room temperature. A main excitation peak (359 nm) of 2 appears under red emission of 615 nm. By contrast, all emission peak intensities of 1 were enhanced by addition of gadolinium(III), and the 545 nm band is much stronger than the 615 nm band, attributed to, under perturbation of the ligand field, the probability of ⁵D₄ → ⁷F₃ transition of Tb(III) was greatly enhanced in 2. Because of perturbation of the ligand field by addition of gadolinium(III), the probability of ⁵D₄ → ⁷F₅ transition of Tb(III) was greatly enhanced in 1 and green fluorescence was observed. The antibacterial activity showed that the two complexes were active against Escherichia coli, Staphylococcus aureus and Bacillus subtilis.     

Synthesis and crystal structures of lanthanide complexes with foliage growth regulator: phenoxyalkanoic acid

Reactions of Ln(ClO₄)₃?·?6H₂O (Ln=La(III), Eu(III), Nd(III)), 1,10-phenanthroline (phen) and phenoxyacetic acid (PA) or 2,4-dichlorophenoxyacetic acid (2,4-D) yield [La(PA)₂ (phen)₂]₂(ClO₄)₂ (1), [Eu(2,4-D)₂(phen)₂]₂(ClO₄)₂ (2) and [Nd(2,4-D)₃(C₂H₅OH)] _n (3). Compounds 1–3 are characterized by elemental analyses, IR, UV–Vis, ESI-MS spectra and TGA. 1 is also characterized by ¹H and ¹³C NMR. Single crystal X-ray diffraction analyses reveal that 1 and 2 are binuclear, and 3 has a one-dimensional polymeric structure. The La(III), Eu(III) and Nd(III) are nine-coordinate with a distorted tricapped trigonal-prism geometry.     

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.