Synthesis and Structure of a Novel Rare Earth Complex: Eu3(dpa dioxide)4·(CF3COO)5·H2O

The novel europium complex Eu3(dpa dioxide)4·(CF3COO)5·H2O (dpa dioxide = di-2-pyridylamine N,N'-dioxide) was prepared by the reaction of Eu(CF3CO2)3 with Dpa dioxide in acetonitrile under 95 ℃ and determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 41.632(8), b = 14.662(3), c = 23.300(4)(A),β= 100.862(5)°, Z = 8, D = 1.775 g/cm3, V = 13968(4)(A)3, F(000) = 7232, the final R = 0.0464 and wR = 0.1168. In this tri-nuclear complex, each europium(Ⅲ) is nine-coordinated to adopt an unequal sphere geometry.     

Synthesis and Structure of a Novel Rare Earth Complex: Eu_3(dpa dioxide)_4·(CF_3COO)_5·H_2O

The novel europium complex Eu3(dpa dioxide)4·(CF3COO)5·H2O (dpa dioxide = di-2-pyridylamine N,N'-dioxide) was prepared by the reaction of Eu(CF3CO2)3 with Dpa dioxide in acetonitrile under 95 ℃ and determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 41.632(8), b = 14.662(3), c = 23.300(4) , β = 100.862(5)o, Z = 8, D = 1.775 g/cm3, V = 13968(4) 3, F(000) = 7232, the final R = 0.0464 and wR = 0.1168. In this tri-nuclear complex, each europium(Ⅲ) is nine-coordinated to adopt an unequal sphere geometry.     

A Porous 3D Supramolecular Architecture of Cd（II） Complex with Water Clusters as Pillars

A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.     

A Zinc（II） Coordination Polymer Possessing a Linear Trinuclear Building Block [Zn3（CO2）6N2]

A new coordination polymer [Zn3（bpda）3（bpy）] 1 （H2bpda = 2,2＇-biphenyldicar- boxylic acid, bpy = 4,4＇-bipyridien） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, TG analysis and IR spectrum. 1 Crystallizes in cubic crystal system, space group Ia 3, with a = 20.9687（9） A, V = 9219.7（3） A^3, Z = 8, and R（I 〉 2σ（I）） = 0.0431. Complex 1 is a three-dimensional framework involving a new building block, linear trinuclear {Zn3（CO2）6N2} cluster. In the structure, each bpda coordinates to four zinc atoms via its two bridging bidentate carboxylate groups. To the best of our knowledge, 1 implies a new coordination mode of 2,2＇-biphenyldicarboxylic acid. The solid state fluorescent spectra show a strong emission peak at 451 nm （λex= 341 nm）.     

A Potassium Organic-inorganic Hybrid Complex with Channels Hosting Decorated Poly-anion Chains

A potassium organic-inorganic hybrid complex {H2[K（PMo12O40）（CH3CN）3]- （dpdo）2（H2O）}n 1 （dpdo = 4,4＇-bipyridine-N,N＇-dioxide） with special channels for the chain-like assembly of decorated Keggin-type anions was synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group Cmcm with a = 20.5328（17）, b = 16.8877（14）, c = 16,1454（14） A, V = 5598.4（8） A^3, Z = 4, C26H29N7O45KMo12P, Mr= 2380.91, Dc = 2.825 g/cm^3,μ = 2.813 mm^-1, F（000） = 4528, the final R = 0.0324 and wR = 0.0880 for 2577 observed reflections with I 〉 2σ（I）. Compound 1 exhibits a 3D network structure with large channels hosting decorated poly-anion chains as guests.     

Synthesis, Crystal Structure and Properties of a Europium Complex with 3-Iodobenzoic Acid and 2,2＇-Bipyridine

The complex [Eu（3-IBA）3·2,2＇-bipy]2 was synthesized from 3-iodobenzoic acid （3-HIBA）, 2,2＇-bipyridine （2,2‘-bipy） and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group Pi, with a = 10.958（2）, b = 12.311（3）, c = 12.556（3） A, α = 81.549（3）, β = 82.404（4）, γ = 78.348（3）°, Mr = 1049.15, V= 1631.7（6） A3, Z = 1, Dc = 2.135 g/cm^3, F（000） = 980, 2（MoKa） = 0.71073 A,μ（MoKa） = 4.804 mm^-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I 〉 2σ（I）. The Eu（Ⅲ） ion is eight-coordinated and two Eu（Ⅲ） ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.     

脱铁伴清蛋白两结合位点不同酪氨酸氢键的特性

The interaction of gallium（Ⅲ） with the ligands containing phenolic group（s）, such as salicylic acid, 8-hydroxyquinoline, N,N＇-bis（2-hydroxybenzyl）ethylenediamine-N,N＇diacetic acid （HBED）, N,N＇-ethylenebis[2-（o- hydroxyphenyl）glycine （EHPG）, and ovotransferrin, was studied, respectively, by means of fluorescence in 0.01 mol/L Hepes at pH 7.4 and room temperature. Fluorescence intensity showed an increase when gallium（Ⅲ） was bound to 8-hydroxyquinoline and HBED. In contrast, it was decreased with the interaction of gallium（Ⅲ） with salicylic acid and EHPG. At pH 7.4, there was N…H-O type intramolecular hydrogen bond in the former, and the latter existed O…H-O type intramolecular hydrogen bond. Fluorescence titration of apoovotransferrin with gallium（Ⅲ） displayed that the fluorescence intensity was decreased at the N-terminal binding site, while enhanced at the C-terminal binding site. It can account for the O…H-O type intramolecular hydrogen bonds for the phenolic groups of Tyr92 and Tyr191 residues at the N-terminal binding site. And there are N…H-O type intramolecular hydrogen bonds for Tyr431 and Tyr524 residues at the C-terminal binding site. In addition, under the same conditions, the conditional binding constant of gallium（Ⅲ） with EHPG or HBED determined by fluorescence method is lg KGa-EHPG=19.18 or lg KGa-HBED= 19.08.     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Novel Polyoxometalate [H6MoVI8O27]·3C4N2H10

A new infinite three-dimensional framework structure of the title compound [H6Mo^VI8O27]·3C4N2H10 has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent spectra and single-crystal X-ray diffraction. C12H36Mo8N6O27 crystallizes in the triclinic system, space group P1^- with a = 8.820（3）, b = 9.534（3）, c = 10.993（4）A, α= 99.985（17）, β = 106.65（2）, γ= 101.650（14）°,V = 840.6（5）A^3, Mr = 1463.99, Z = 1, Dc = 2.892 g/cm^3,μ = 2.993 mm^-1, F（000） = 702, the final R = 0.0676, wR = 0.1920 and S = 1.074 for 2196 observed reflections with I 〉 2σ（I）. The title compound exhibits a novel infinite three-dimensional （3D） framework composed of a [H6Mo^VI8O27] subunit and three dissociated piperazine fragments. The complex exhibits two strong fluorescent emission bands at ca. 417 and 440 nm （λex = 378nm） in the solid state at room temperature.     

A Novel Complex of Na（I）-Nitronyl Nitroxide [Na（NIT- 1＇-MeBzIm）3]ClO4： Synthesis and Crystal Structure

A novel complex [Na（NIT-1＇-MeBzIm）3]ClO4 （NIT-1＇-MeBzIm = 2-{2＇-[（1＇- methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction methods. The title complex crystallizes in trigonal, space group P3 and Z = 2. Crystal data： C45H57ClN12NaO10, Mr = 984.47, a = 13.9411（8）, b = 13.9411（8）, c = 14.8622（16） A, γ= 120°, V= 2501.5（3） A^3, Dc = 1.307 g/cm^3, μ（MoKα） = 0.152 mm^-1, F（000） = 1038, R = 0.0637 and wR = 0.1813 for 1957 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the Na（I） ion is six-coordinated with three NIT-1＇-MeBzlm radicals. As we know, three radicals coordinating to the Na（I） ion in the main group by a chelate way is the first example. The Na（I） ion resides in a distorted octahedron with a facial configuration. Meanwhile, the intermolecular weak interactions result in a 2-D double layer conformation where the uncoordinated perchlorate anions are inserted in the packing space and take part in the H-bond interactions, and each complex is connected with six neighboring complexes and three perchlorate anions.     

The Study on the Stability Constant and Species Distribution of Eu （Ⅲ） and Tb （Ⅲ） Complexes with BDBPH

The stability constants and species distributions of complexes of two lanthanide ions, Eu（Ⅲ） and Tb（Ⅲ）, with a macrocyclic ligand, BDBPH, in 1：1 and 2：lsystem, were determined potentiometrically at 25.0 ℃ and I=0.100 mol L^-l. The two metal ions could form deprotonated mono- or dinuclear complexes with BDBPH after the first two protons of the ligand completely neutralized. At higher pH values, Eu（Ⅲ） could not form hydroxy complexes with BDBPH, while Tb（Ⅲ） could form hydroxy complexes in the type of M2L（OH）, M2L（OH）2, and M2L（OH）3.     

Electrospinning Synthesis and Photoluminescence Properties of SnO2：xEu3＋ Nanofibers

NnO2：xEu3＋（x=O, 1%, 3%, 5%, molar fraction） fibers were synthesized by electrospinning technology. The size of the as-prepared fibers is relatively uniform and the average diameter is about 200 nm with a large draw ratio. The as-prepared Eu3＋ doped SnO2 nanofibers have a rutile structure and consist of crystallitc grains with an average size of about 10 nm. A slight red shift of the A1gand Bag vibration modes and an additional peak at 288 nm were observed in the Raman spectra of the nanofibers. The energies of bandgaps of the SnO2 nanofiber with Eu doping of 1% and 3% are 2.64 eV, and the energy of bandgap is 2.94 eV with Eu doping of 5%（molar fraction）. There is only orange emission（5D0→7F1 magnetic dipole transition） for Eu doped SnO2 nanofibers, and no red emission could be observed. The orange emission upon indirect excitation splits into three peaks and the peak intensity at the excitation wavelength of 275 nm is higher than that at the excitation wavelength of 488 nm.     

Synthesis,Structure, Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[ CdLu-（4,4＇-dps） ]2（H2O）2]＇（4＇abs ）2（H2O）2

A new cadmium（N） compound, {[ CdLu-（4,4＇-dps） ]2（H2O）2]＇（4＇abs ）2（H2O）2n 1 （4,4＇-dps = 4,4＇-dipyridylsulfide, 4-abs = deprotonated 4-amino benzenesulfonic acid）, has been synthesized and structurally characterized. It belongs to the orthorhombic system, space group Pbcn with a = 19.950（3）, b = 10.6381（13）, c = 18.055（2）A, V= 3831.8（8） A3, Z = 4, C32H36CdN6010S4, Mr = 905.31, F（000） = 1848, μ= 0.850 mm^-1, Dc = 1.569 Mg/m^3, the final R = 0.0238 and wR = 0.0589 for 3080 observed reflections with I 〉 2σ（I）. Complex I is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation, uncoordinated 4-aminobenzene sulfonate anions and water molecules. The cadmium（H） ion adopts a six-coordinate distorted octahedral geometry. Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O-H…O and N-H…O hydrogen bonds together with electrostatic force. The cyclic voltammograms and fluorescence spectrum of 1 were also measured. It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.     

Synthesis,Crystal Structure and Photoluminescent Properties of a New Dinuclear Copper（Ⅰ） Complex [Cu2（μ2-dppm）2（MeCN）2（μ2-MeCN）]（ClO4）2·MeCN

The title compound [Cu2（μ2-dppm）2（MeCN）2（μ2-MeCN）]（ClO4）2·MeCN （dppm = bis（diphenylphosphino）methane） has been prepared and characterized. It crystallizes in the monoclinic system,space group P21/n,with a = 11.904（6）,b = 20.755（11）,c = 24.744（13）A,β = 98.226（12）°,C58H56Cl2Cu2N4O8P4,Mr = 1258.93,V = 6051（5） A^3,Z = 4,Dc = 1.382 g/cm^3,μ = 9.52 mm^-1,F（000） = 2592,R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I 〉 2σ（I）. Each Cu（I） center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands,one nitrogen atom from a terminally coordinated acetonitrile molecule,and another nitrogen atom from a μ2-acetonitrile molecule. The two Cu（I） centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a ＇chair-like＇ configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm.     

Synthesis,Crystal Structure and Fluorescent Property of 2,2＇-Bipyridyl-3,3＇- bis（N,N＇-disalicylidene）-formyhydrazone

A binicotinic biscarbohydrazone compound,2,2＇-bipyridyl-3,3＇-bis（N,N＇-disali- cylidene）-formyhydrazone,1 has been prepared and characterized by elemental analysis,FT-IR,1H- NMR,ESI-MS and single-crystal X-ray diffraction analysis. The crystal belongs to triclinic,space group P1 with a = 9.419（3）,b = 11.745（4）,c = 12.035（5）A,V = 1178.8（7）A^3,Z = 2,Dc = 1.354 g/cm^3,μ = 0.095 mm^-1,F（000） = 500,λ（MoKα） = 0.71073 ,C26H20N6O4,Mr = 480.48,the final R = 0.0480 and wR = 0.1084 for 3634 observed reflections with I 〉 2σ（I）. Single-crystal X-ray diffraction analysis reveals that a 1D supramolecular structure of 1 has been constructed by multiply intermolecular N–H···N and O–H···O H-bonding interactions. Besides,compound 1 exhibits a strong green-light emission in the solid state at room temperature.     

A 3-D Supramolecular Network with 1-D Cation Metal.organic Coordination Polymers and Diverse Motifs from Hydrogenbonded [M（H2O）4]-Carboxylates

One-pot solvothermal reaction of Iransition metal Znn salt with 4,4-bipyddyl （bpy） and 1,4-benzenediacrylic add （H2L） in the presence of Et3N generates a three-dimensional （3-D） supramolecular network with 1-D cation metal-organic coordination polymer, [Zn（H20）a（bpy）]-L 1, and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent property. The complex crystallizes in triclinic, space group P1 with a = 7.1291（2）, b = 7.3784（3）, c = 10.5042（3）A, α = 95.049（2）, β = 102.162（2）, 7 = 97.027（3）0, V= 532.38（3）A3, C22H24N2O8Zn, Mr = 509.82, De= 1.590 g/cm3, p（MoKa）= 1.207 ram-l, F（000） = 264, Z = 1,the finalR=O.0438and wR=O.lOll for 1589 observed reflections （I 〉 2σ（I））. In the crystal structure, the second building unit composed of [Zn（H2O）4].L constructs two distinct 2-D supramolecular sheets and a neutral 3-D architecture. The title compound 1 shows strong photoluminescence with emission maximum at 2 = 455 nm upon λex.max = 355 nm.     

Urothermal Synthesis,Crystal Structure,and Luminescent Property of a New Zn（II） Coordination Polymer Constructed from Terephalic Acid and 5-Methyl-1H-tetrazole Ligands

A new luminescent Zn（II） compound, [Zn（pbdc）0.5（mtz）（DMPU）]n （1,H2pbdc = terephthalic acid, Hmtz = 5-methyl-1H-tetrazole, DMPU = N,N＇-dimethylpropyleneurea）, has been urothermally synthesized and characterized by elemental analysis, IR, X-ray powder diffraction （PXRD） and single-crystal X-ray diffraction. The title compound crystallizes in orthorhombic Pbca space group with α = 17.2649（5）, b = 10.4680（3）, c = 17.4457（7） ？, V = 3152.94（18） ？3, C12H17N6O3Zn, Mr = 358.71, Z = 8, Dc = 1.511 g/cm3, F（000） = 1480, μ = 1.579 mm-1, the final R = 0.0379 and wR = 0.0971 for 2785 observed reflections （I 〉 2σ（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a 2D undulated layer with a 3-connected hcb topology. Moreover, the luminescent properties of 1 have also been investigated in the solid-state at room temperature.     

Synthesis and Crystal Structure of 3,3 ＇-（2,2 ＇-（E thane- 1,2-diylbis（oxy） ） bis（ethane- 2,1- diyl））bis（2-（4-chlorophenylamino）quinazolin-4（3H）-one）

The title compound 3,3＇-（2,2＇-（ethane-1,2-diylbis（oxy））bis（ethane-2,1-diyl））bis（2- （4-chlorophenylamino）quinazolin-4（3H）-one） 3 （C34H30CI2N604, Mr = 657.54） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in space group P1 with a = 9.9185（8）, b = 10.6124（9）, c = 15.4064（13） A, α = 92.896（2）,β = 103.813（2）, γ= 94.635（2）°, V= 1565.5（2） A3, Z = 2, Dc = 1.395 g/cm^3,μ = 0.257 mm^-1, F（000） = 684, the final R = 0.0580 and wR = 0.1284 for 3400 observed reflections （I〉 2σ（I）. It remains triclinic in the crystal. Intra- and intermolecular N（3）-H（3A）…O（2）, N（6）-H（6A）…O（3） and C（19）-H（19A）…O（4） #1 （#1： 1-x, 1-y, -z） hydrogen bonds are observed in the title compound. A two-dimensional chain network is formed from the dimmers and intermolecular π-π interactions in the crystal structure. This open network has solvent-accessible voids （10A3）.     

Crystal Structure and Magnetic and Fluorescent Properties of a New Copper（II） Complex Cu2（L）4（2,2＇-bipy）2（H2O）2

A new copper（II） complex Cu2（L）a（2,2＇-bipy）2（H2O）2 （1） has been synthesized with 2-benzoylbenzoic acid （HL） and 2,2＇-bipyridin as ligands. The crystal belongs to a monoclinic system with space group Cc, a = 13.9979（II）, b = 15.9888（13）, c = 30.306（3） A, β = 100.8700（10）°, V= 6661.1（10） A3, Dc= 1.372 g/cm3, Z = 8, F（000） = 2840, the final GOOF = 1.018, R= 0.0685, and wR= 0.1731. There are two mononuclear Cu（L）2（2,2＇-bipy）（H20） units in the crystal of 1. Each Cu（II） cation is coordinated by five atoms. The magnetic and fluorescent properties of 1 were studied. The results show that 1 exhibits weak paramagnetism, and when the excitation wavelength is at 616 nm, it has an intense fluorescent emission band around 482 nm.     

A 2-Fold Interpenetrated Framework Assembled from Pyridine-3-carboxylate Ligand and Transition Metal:Synthesis,Structure and Photoluminescent Property

A novel cadmium（Ⅱ） coordination polymer [Cd2（3-pa）4（4,4＇-bpy）（H2O）].3.08H2O 1 has been synthesized by pyridine-3-carboxylate （3-pall） and CdO with exo-bidentate rigid dipyridyl ligand 4,4＇-bipyridine （4,4＇-bpy） by using a hydrothermal method, its structure was determined by single-crystal X-ray diffraction and its luminescent property was also documented. Complex 1 crystallizes in orthorhombic space group Pbcn with a = 21.4074（14）, b = 27.1119（18）, c = 12.3879（8） A, V = 7189.9（8） A3, Z = 8, C34H32.16Cd2N6O12.08, Mr= 942.85, Dc = 1.742 g/cms, p = 1.255 mm-1 and F（000） = 3766. The structure was solved by direct methods and refined to R = 0.0353 and wR = 0.0891 for 6278 observed reflections （I 〉 2σ（I））. The most prominent structural feature is the mutual interpenetration of two identical 3-D open frameworks via filling the large void space, which gives a 2-fold interpenetrating architecture during the self-assembly process.     

Synthesis and Structure of a POMs-based 3D Zeolike Ionic Crystal, {[Co（dpdo）2（H2O）2（CH3CN）]2（SiMo12O40）（H2O）2}n

A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.