Luminescent Properties of Terbium（Ⅲ） and Europium（Ⅲ）Complexes with Six 4-Acetyl-bispyrazolones

The lowest triplet energy levels of the six ligands（T） were determined to be 22989 cm-1[1,3-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,3-propanedione,BPMPTD],23148 cm-1[1,4-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,4-butanedione,BPMPBD],23419 cm-1[1,5-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,5-pentane-dione,BPMPPD],23310 cm-1[1,6-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-1,6-hexanedione,BPMPHD],21978 cm-1[1,9-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazolon-4＇）-l,9-nonanedione,BPMPND] and 21930 cm-1[1,10-bis-（1＇-phenyl-3＇-methyl-5＇-pyrazoion-4＇）-1,10-decanedione,BPMPDD],respectively.It was explained satisfactorily that the six ligands are more efficient for sensitizing the luminescence of Tb3＋ than that of Eu3＋ at room temperature,and the order of the luminescent intensities for the Tb3＋ complexes is explained by the relative energy gap between T and 5DJ of Tb3＋ or Eu3＋.As a conclusion,when 2700 cm-1＜△E（T-5D4）＜3000 cm-1,the luminescent intensity of the Tb3＋ complex is the strongest.This means that the lowest triplet energy level of the ligand is a chief factor to dominate RE3＋luminescence.     

Dioxygen Affinities and Catalytic Oxidation Performance of Cobalt （Ⅱ）Complexes with N—Aryl Hydroxamic Acid

The oxygenation of cobalt(Ⅱ) hydroxamates(CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined.The effects of X and Y bonded to hydroxamate group on dioxygen affinities and catalytic oxidation performance were also investigated.     

Synthesis of TiO2 Nanoparticles via a Ti（IV） Complex with Stearic Acid and the Photocatalytic Activity for Organic Oxidation

The nano-sized particles of TiO2 were prepared by thermal decomposition of titanium (IV) tetrabutanoxide complex with stearic acid at 450℃ in the air.It was observed that the amount of stearic acid,used initially for the complex synthesis in 2-propanol at 25℃,had great influence on the physical properties of the prepared TiO2 including crystal structure, the particle size,surface area and the adsorption capacity for organic substrate of a textile dye X3B in eater,and thereafter the photocatalytic activity for the dye oxidation.Some samples displayed lower adsorption capacity for the organic substrate in water than a TiO2 of Degussa p25,but higher photocatalytic activity for the organic oxidation.Possible reason for the observed difference was discussed in the text.     

Synthesis of Eu（Ⅲ） and Tb（Ⅲ） Complexes with Two New Amide Type Podands and Their Luminescence Properties

Two new amide type podands L1 and L2 (L1=1,1,1-tris{[2-benzylaminoformyl)phenoxyl] methyl} propane,L2=1,3,5-timethyl-2,4,6-tris{[2-benzylaminoformyl)phenoxyl]methyl} benzene)and their europium and terbium nitrates complexes were synthesized.The luminescence properties of these complexes were also studied.     

Thermodynamic Stability Research of Metal Complexes with a Tripodal Amide Ligand and Crystal Structure of its Cobalt（Ⅲ） Complex

A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).     

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.     

Synthesis, Characterization, Spectroscopic and Electrochemical Properties of New Mono- and Binuclear Copper（Ⅰ） Complexes with Substituted 2,2′-Bipyridine

The mono- and binuclear Cu(Ⅰ) complexes with substituted 2,2′-bipyridine and iodide ligands, [CuL2]BF4(L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2′-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2′-bipyridine (b) and 6-(4-methoxylphenyl)-2,2′-bipyridine (c)) and [Cu2(μ-I)2L2] were prepared, and the crystal structures of the complexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nrn. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(Ⅰ) state.     

Syntheses and Structures of Two Mixed Ligands Lanthanide Complexes with N,N—Substituted Adipamide

1 INTRODUCTIONInstead of the traditional organo-phosphate or phosphorus extractents which ultimately create undesirable waste even after incineration [1], some organic amides[2] have been suggested as possible extractents for the separation of lanthanides, such as (R1R2NCO)2(CH2)n [3,4]. As excellent ligands, diamides show stability, low toxicity and can be synthesized by simple methods. Hudson and his colleagues have synthesized a series of malondiamides and studied the structures of t…     

Syntheses and Crystal Structures of Ternary Complexes of Zinc（Ⅱ） and Cadmium（Ⅱ） with 3-Aminobenzoic Acid and 1,10-Phenanthroline

1 INTRODUCTION Benzoic acids with substituent of amino are a class of rigid ligands possessing several functional groups. When they coordinate to metal ions, versa- tile coordination modes will be presented with pre- sence of not only coordinate-covalent bonds but also hydrogen bonds. Besides, diverse coordination modes of carboxyl and rigid frame of benzene ring gua- rantee the stability of multi-dimensional structures of the synthesized metal complexes. Thus ligands of this class are o…     

Synthesis and Spectra Analyses of Eu（lll） Binary Complexes with Polycarboxylic Acid

分别以1,3,5-苯三甲酸（H3BTC）、苯六甲酸（H6MTA）和1,2,3,4,5,6-环己六甲酸（H6CCA）为配体合成了Eu（Ⅲ）的二元发光配合物Eu（BTC）2H2O,Eu2（MTA）4H2O和Eu2（CCA）4H2O.通过元素分析、红外光谱和等离子体原子发射光谱对其化学组成进行了结构表征,表征结果与理论吻合良好.利用荧光分度计,研究了所制备配合物室温条件下的荧光性能（荧光激发光谱、发射光谱、荧光寿命和量子效率）,结果表明：该三种配合物在紫外光照射下,均发射Eu（Ⅲ）离子的特征红光,其中Eu2（MTA）4H2O（量子效率=10.25%,荧光寿命=0.36 ms）的荧光性能最好,这说明配体H6MTA的能级与Eu3＋离子能级匹配程度很好.另外,通过热分析对配合物的热稳定性进行了分析,结果表明：该三种配合物均具有良好的热稳定性,主要分解温度远高于其他β-二酮配合物.     

Synthesis and Characterization of Novel Orange-emitting Iridium（Ⅲ） Complexes with Diphenylquinoline Ligands Containing Fluorinated Substituent

Three new cyclometalated iridium（m） complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis （EA）, ^1H NMR, and mass spectroscopy （MS）. The photophysical and electrophosphorescent properties of the complexes were briefly discussed.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln（DMSO）2（H2O）（μ-CN）4Fe（CN）2] （Ln = Ce and Eu,DMSO = Dimethylsulfoxide） with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln（DMSO）2（H2O）（μ-CN）4Fe（CN）2] （Ln = Ce 1, Eu 2） have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1： C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852（4）, b = 10.729（5）, c = 11.181（5）A,β = 96.992（8）°, V = 935.0（7） A^3, Z = 2, Dc = 1.870 g/cm^3,/1 = 3.421 mm^-1, F（000） = 512, R = 0.0363 and wR = 0.0971; and those for 2： C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P21n, a = 7.739（5）, b = 10.668（7）, c = 11.008（7） A,β = 96.943（3）°, V = 902.1（11） A^3, Z = 2, Dc = 1.981 g/cm^3,/1 = 4.499 mm^-1, F（000） = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe（Ⅲ） ion is in a nearly regular octahedral environment. The title complexes can be described as two- dimensional （2-D） stair-like structures, which are further connected by hydrogen bonds to form three-dimensional （3-D） frameworks.     

Synthesis and Characterization of aLead（Ⅱ）Complex with MicroporousStructure

1 INTRODUCTION Recently, much interest has been focused on various extended framework due to their intriguing architectures, new topologies and potential applications in microelectronics, nonlinear optics, molecular selection, ion exchange and catalysis[1~4] . In the last few years, a wide range of infinite structures with diverse topologies has been prepared by the reaction of metal ions with mulriple organic ligands[5～9]. However, up to now, much of the work has been concentrated on c…     

Syntheses and Crystal Structures of Two New Main Group Metal Complexes （M = Al, Bi） with the Substituted p-Hydroquinones

The title complexes [Al(Hcah)(H2O)2]·2H2O (A) and [Bi(Hcah)(H2O)]n (B), where H4cah = 2-[N,N-bis(carboxymethyl)aminomethyl] hydroquinone, have been synthesized and characterized using X-ray single-crystal structure determination, IR and elemental analysis. Both complexes crystallize in the monoclinic system, space group P21/c with a = 7.8660(16), b = 10.096(2), c = 19.053(4) and β = 93.50(3)° for A; and those for B: a = 9.2348(18), b = 7.9061(16), c = 17.141(3) and β = 102.64(3)°. In addition, further investigation revealed that the central Al(III) ion in the mononuclear complex A is in a distorted octahedral coordination geometry, while structural analysis reveals that the Bi(III) ion is in a distorted pentagonal bipyramid, forming a 2-D polymeric complex B, and the coordination network is a 2D 4.82 net. The TG analyses of A indicate two steps of water loss.     

Synthesis of N—（4—Salicylideneiminoaryl）monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt（Ⅱ）Complexes

The Schiff base‐containing pendant monoaza crown ether HL¹, HL², HL³ and HL⁴ have been synthesized by condensation of salicylaldehyde with N‐(4‐aminoaryl) monoaza crown ethers, which were prepared conveniently from 4‐nitro‐N, N‐di(hydroxyethyl) aniline or 4‐nitrobenzyl chloride via cyclization or condensation and reduction. The structures of HL¹—HL⁴ were verified by ¹H NMR, IR spectra, MS and elemental analysis. Moreover, the oxygenation constants (KO2) and thermodynamic parameters (δH⁰ and δS⁰) of their cobalt(II) complexes were determined in the range of ?5 °C to 25 °C, and the effect of crown ring bonded to a Schiff base on the dioxygen affinities of cobalt(II) complexes was also observed as compared to the uncrowned analogue (CoL).