Synthesis and characterization of terbium(Ⅲ)-pyromellitic acid(H_4L)-1,10-phenanthroline (phen) luminescent complex

The terbium(Ⅲ)-pyromellitic acid(H4L)-1,10-phenanthroline(phen) luminescent complex was synthesized using a co-precipitation method.The chemical composition of the synthesized complex was speculated to be Tb4L3(phen)0.075·10H2O by elemental analysis,inductively coupled plasma-atomic emission spectroscopy(ICP-AES),and Fourier-transform infrared spectroscopy(FT-IR).The X-ray diffraction analytic results indicated that the synthesized complex is a new crystalline complex,whose structure was different from those of other two ligands.The scanning electron microscopy analytic results showed that the product was of spherical crystals with good dispersion property,and the mean diameter of the spheres was about 1-2 μm.The TG-DTA result showed that the complex had good stability below 489 °C.PL spectra showed that the complex emitted characteristic green fluorescence of Tb(Ⅲ) ion under ultraviolet excitation.

Preparation, Characterization and Luminescent Properties of MCM-41 Type Materials Impregnated with Rare Earth Complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

Syntheses,Structures,and Luminescent Properties of New Zn~Ⅱ-Y~Ⅲ and Zn~Ⅱ-Ln~Ⅲ Schiff Base Complexes

Eight new ZnⅡ-yⅢ and ZnⅡ-LnⅢ heterometallic Schiff base complexes： MZnL2（NO3）3 （M = Y （1）, La （2）, Pr （3）, Nd （4）, Eu （5）, Gd （6）, Dy （7）, Er （8）; L = 2-（（（2- （imidazo[1,5-a]pyridin-3-yl）phenyl）imino）methyl）-6-methoxyphenol）, have been rationally synthesized under solvothermal conditions and characterized by IR, elemental analyses （EA）, single-crystal X-ray diffraction, and powder XRD. Furthermore, luminescence in the visible region for solids 1-8 suggested zine/ligand-centered emission at room temperature.

Hydrothermal Synthesis, Crystal Structure and Luminescence Properties of a New 2D Cadmium Complex Based on the 4,4'-Bis(benzimidazol-1-ylmethy1)biphenyl and Glutaric Acid Ligands

A new polymeric complex {[Cd2（bbmb）2（gt）2]＇（H2O）2}, （bbmb = 4,4＇-bis（benzimidazol-l-ylmethyl）biphenyl, H2gt = glutaric acid） has been obtained by hyclrothermal method and structurally characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray diffraction. The complex belongs to the triclinic system, space group P1 with a = 10.2417（15）, b = 13.752（2）, c = 22.201（3） A, a = 73.899（2）, β = 88.416（2）, y = 78.305（2）°, V = 2940.4（7） A3, Z = 2, C66H56Cd2N808, Mr = 1313.99, Dc = 1.484 g/cm3, F（000） = 1336 and μ = 0.787 mm-1, and features a 2D network. In the solid state at room temperature, the cadmium（Ⅱ） complex exhibits strong fluorescence absorption at 435 nm （λmax）.

Synthesis, Crystal Structure and Luminescent Property of Ladder-shaped Zinc Coordination Polymer with Mixed Polyfunctional Ligands

One new Zn（Ⅱ） complex [Zn2（cptpy）2（tzba）（H2O）]·H2O（1, Hcptpy = 4-（4-carboxyphenyl）-2,2＇：4＇,4＇＇-terpyridine（Hcptpy）, H_2tzba = 4-（tetrazol-5-yl）benzenecarboxylic acid） has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction techniques. It is formulated as C52H36O8N10Zn2, crystallizes in monoclinic system, space group P21/c with α = 15.1599（13）, b = 28.083（2）, c = 10.9039（9） A, b = 97.517（8）o. V = 4602.3（6） A^3, Z = 4, Mr = 1059.68, Dc = 1.529 g/cm^3, F（000） = 2168 and μ = 1.112 mm^-1. The final R = 0.0831 and wR = 0.2143 for 8458 observed reflections with I 〉 2s（I）. The assembly of polyfunctional organic ligands Hcptpy and H_2tzba with Zn（II） atoms resulting in a rare example of double-edge ladders, which is further extended into a 3D supramolecular network via O–H…O/N hydrogen bonds. In addition, thermal gravimetric analysis（TGA） and PXRD patterns for 1 were studied. Photo luminescent property of 1 was also investigated.

Structure and Luminescence Property of a Linear Tetranuclear Gold(Ⅰ)-thiolate Complex through Au-Au Interaction

The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The complex crystallizes in monoclinic space group C2/c with a=26.785（7）,b=25.654（6）,c=12.277（3）A,β=106.879（5）°,V=8073（4）A^3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm^3,F（000）=4592,Rint=0.0529,T=293（2）K,μ=8.157 mm^（-1）,the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I〉2σ（Ⅰ）.The intramolecular and intermolecular Au¨Au distances are 2.8670（9）and 3.2367（9）A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.

Syntheses, Structure and Properties of a Strontium(Ⅱ) Complex with 5-Sulfoisophthalic Acid Monosodium

A new Sr（Ⅱ） complex, [Sr（Hsip）（H2O）] （1, NaH2sip = 5-sulfoisophthalic acid monosodium）, has been synthesized by solvothermal reaction of SrCO3 and NaH2sip at 120 ℃, and characterized by single-crystal X-ray diffraction studies, elemental analysis and FT-IR. Single- crystal X-ray diffraction reveals that compound 1 has a 3D architecture, and there is only one crystallographically independent Sr（Ⅱ） ion in 1. The coordination geometry of Sr（Ⅱ） is a distorted tetragonai anti-prism. The whole Hsip2- ligand performs aμ6-coordination model. In the solid state, complex 1 shows luminescence with the maximum emission intensity at 417 nm upon excitation at 320 nm. Thermal stability of complex 1 was also investigated.

Cadmium(II)-1,4-phenylenediacetate Complex with Green Luminescence

The title complex, formulated as {[Cd（pda）（phen）]·3H2O}, 1 （pda = 1,4-phenylenediacetate, phen = 1,10′-phenanthroline）, has been hydrothermally synthesized and determimned by X-ray crystallography. Crystallographic data： triclinic, space group P1^-, a = 10.375 （7）, b = 10.435（1）, c = 12.040（1） A.α = 68.503（1）, ,β= 86.371（1）, γ= 66.231（1）°, Mr = 538.82, V = 1104.5（8） ,A^3, Z = 2, Dc = 1.620 g/cm^3,μ = 1.035 mm^-1, F（000） = 544, the final R = 0.0380 and wR = 0.0985 （w = 1/[σ^2（F0^2） ＋ （0.0559P）^2 ＋ 1.5319P], where P = （F0^2＋ 2Fc^2）/3） based on 3444 observed reflections with I 〉2σ（I）. Complex 1 features a two-dimensional layer. Fluorescent analysis reveals that it exhibits intense green luminescence with the maximum at around 516 nm.

Crystal Structure and Luminescent Properties of[Cu(phen)_2I][Bi(phen)I_4]

The title complex, [Cu（phen）2I][Bi（phen）I4], has been successfully synthesized by a solution method. Its crystal structure was determined by X-ray diffraction method, and crystallizes in triclinic, space group P1 with a = 10.3876（2）, b = 14.4258（5）, c = 14.7128（5） ？, α = 82.569（8）, β = 73.442（7）, γ = 79.299（8）°, V = 2069.68（11）A3, Z = 2, Dc = 2.323 g/cm3, F（000） = 1318, μ（Mo Kα） = 13.132 mm–1 and T = 293（2） K. The final R = 0.0472 and w R = 0.1147 for 6027 observed reflections with I 〉 2σ（I）. In the structure of the title compound, [Bi（phen）I4]– provides us an opportunity to survey the influence of coordination component on the structure of the cation in the [Cu（phen）2I][Y] system. X-ray diffraction and luminescent spectrum study of the complex are also described.

Synthesis,Structure and Photoluminescence of a New Ir Complex Based on Pyridine-2,3-dicarboxylic Acid

A new complex Ir（ppy）2（Hpda）（Hppy=2-phenylpyridine, H2pda=pyridine-2,3-dicarboxylic acid） has been synthesized and characterized. According to single-crystal X-ray diffraction analyses, the title complex crystallizes in the monoclinic system, space group P21/n with a=8.5708（10）, b=22.685（2）, c=12.5722（15） , β=96.19（1）°, V=2430.2（5） 3, C（29）H（20）N3O4 Ir, Mr=666.22, Z=4, Dc=1.833 g/cm3, F（000）=1304, μ=5.54 mm（-1）, λ（Mo Kα）=0.71073 , GOOF=1.02, the final R=0.049 and w R=0.119 for 4680 independent reflections with Rint=0.069. The title complex is of mononuclear structure. Intermolecular C–H···O hydrogen bonds and π-π stacking interactions result in the formation of a 3D supramolecular network. Photoluminescent spectra show that one intense emission band with the maximum of 516 nm can be observed in the title complex.

Evaporable luminescent lanthanide complexes based on novel tridentate ligand

A novel tridentate ligand N-（6-（diphenylphosphoryl）pyridin-2-yl）-2,2,2-trifluoroacetamide （DPPOPFA） was designed and synthesized. Crystal structure of the ligand revealed the ＂keto＂ form of ligand in solid state other than the ＂enor＇ one, and it was also found that two kinds of molecules with different conformations were connected by hydrogen bonding between amide N-H and phos- phoryl P=O. This ionic ligand was used to coordinate a variety of lanthanide ions, forming neutral 3：1 complexes. Absolute overall quantum yields of these complexes in solid states were 36% for Eu（III）, 29% for Tb（III） and 3% for Dy（III） with lifetimes of 1.1, 1.1 and 0.087 ms, respectively. The complexes had excellent thermal stability and did not decompose till 370 ℃. And they could subli- mate in vacuum （1 ×10^-4 Pa） at 330℃ due to the weak molecular interaction.

Synthesis and Characterization of Tb^(3+)-Trimesic Acid Fluorescence System

The luminescent complex of Tb (3+)-trimesic acid was synthesized in an alcohol and water mixed solvent. The chemical components of the complex TbL·5H_2O was characterized by the element analysis,thermal analysis and FTIR. The results of the XRD patterns and SEM photographs indicate that the complex is composed of a lot of bar-shaped crystal grain with 5～10 μm long. The results of the photoluminescence show that the complex emitted the characteristic green fluorescence of Tb (3+).

Synthesis, characterization, biological activities and luminescent properties of lanthanide complexes with [2-thiophenecarboxylic acid, 2-(2-pyridinylmethylene)hydrazide] Schiff bases ligand

A Schiff base L [2-thiophenecarboxylic acid, 2-（2-pyridinylmethylene）hydrazide] with its lanthanide metal complexes was synthesized. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis（NMR, FT-IR, and UV-Vis）, luminescence and thermal gravimetric analysis. The Schiff base ligand was a tridentate chelate and coordinates to the central lanthanide ion with 1：2 metal：ligand ratio. The conductivity data showed a 1：1 electrolytic nature with a general formula [LnL_2（NO_3）_2]NO_3. The luminescence emission properties for Sm, Tb, and Eu complexes were observed and showed that the ligand L could absorb and transfer energy to Sm（III）, Tb（III） and Eu（III） ions. The complexes possessed a good antibacterial activity against different bacterial strains. In addition, the scavenging activity of the Ln（III） complexes on DPPH was concentration dependant and the complexes were significantly more efficient in quenching DPPH than the free Schiff base ligand.

Synthesis and luminescent properties of a silylated-terpyridine derivative and its metalated complexes in solutions and self-assembled monolayers

A silylated-terpyridine（Si TPy） derivative was newly synthesized and reacted with various transition metal ions in the solutions and self-assembled monolayers（SAMs）.Composition and morphology of the SAMs were characterized by using absorption spectra,X-ray photoelectron spectra and atomic force microscope.The silylated-TPy compound gave off a luminescent emission at about 456 nm,which slightly shifted to 452 nm in the Zn^2＋-Si TPy and Fe^2＋-Si TPy metalated complexes.The absorbed energy can be further transferred to lanthanide ions（Tb^3＋and Eu^3＋） to give off the typical emissions of the lanthanide complexes together with an emission of the silylated-TPy at about 363 nm.

Spectral,Thermal and Structural Studies of Two 3D Coordination Polymers Based on Tetracarboxylic Ligand

Two new coordination polymers,[M6L3（DMA）3（H2O）]（M=Zn for 1,Cu for 2,L=tetrakis[3-（carboxyphenyl）oxamethyl]methane acid,DMA = N,N-dimethylacetamide） have been solvothermally synthesized. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 are isostructural and crystallize in the trigonal space group R. The asymmetrical unit contains two metal ions,one L^4- ligand and two coordinated DMA molecules. The metal ions are connected through six aromatic rings into a linear trimetallic zinc building unit. The whole structure is connected through tetrehedral ligand and the trimetallic building units to form a 4,6-connected framework of the toc topology. Compounds 1 and 2 are further studied by IR spectroscopy,thermogravimetric analyses and PXRD. The solid-state UV-Vis and photoluminescent properties of compounds 1 are also investigated.

Organic Light-Emitting Diodes Based on an Iron(III) Complex with Doublet Emission

Because iron is the richest transition-metal element in the earth’s crust,if iron complexes could be used as the emitters in organic light-emitting diodes(OLEDs),the cost of OLEDs would be reduced dramatically.Luminescent iron(III)complexes with low-spin d5 electronic structure theoretically possess spin-allowed doublet metal-to-ligand charge transfer(^(2)MLCT)emission,but little attention has been paid to their application in OLEDs.

Zinc(Ⅱ) coordination architectures based on 5-(1H-tetrazol-1-yl)-isophthalic acid:Synthesis,structures and luminescent properties

With different pyridine-analogs as auxiliary ligands,three novel Zn（Ⅱ） complexes（1-3） based on 5-（1Htetrazol-1-yl） isophthalic acid（H_2L） have been synthesized and structurally characterized.Single crystal X-ray diffraction analyses of complexes 1-3 show the presence of tetrazolyl group,as well as the coordination behavior of the auxiliary ligands as critical factors determining the structures of such Zn（Ⅱ）-carboxyIate coordination architectures.In addition,the resulting complexes all exhibit luminescence properties in the solid state at room temperature.

Tris(Znsalen) cryptand minimizes Znsalen aggregation arising from intermolecular Zn…O interaction

Exploring the factors to control Znsalen aggregation is of importance to design functional materials in catalysis, optical materials and biological imaging. In this work, we synthesized and characterized four cryptand type tri Znsalen complexes and found that cryptand structure could efficiently minimize intermolecular Zn…O interaction. More importantly, encapsulated by PLGA nanoparticles, cryptand tri Znsalen 1 displayed visible intracellular fluorescence whereas monomeric Znsalen 5 could not. These results provide a new access to design new luminescent materials with the potential application in optics and biological studies.