Mixed d/f Complexes Zn(H2L)Ln(NO3)3(Ln=Sm,Tb and Dy)：Crystal Structure,Fluorescence and Thermal Stability

A series of isostructural d/f molecular compounds Zn（H2L）Ln（NO3）3·CH3OH（Ln = Dy（1）, Tb（2） and Sm（3）） were synthesized by the introduction of a designed multifunctional ligand N,N？,N？？,N？？？-tetra（2-hydroxy-3-methoxy-5-methylbenzyl）-1,4,7,10-tetraazacyclododecan（H4L = C（44）H（60）N4O8）. In the isostructural molecules, each crystallographically independent Zn2＋ and Ln3＋ centers are connected by two phenolic oxygen atoms. For the six-coordinate Zn-（2＋） ion, the coordination geometry can be viewed as a regular bicapped square pyramid. While for the ten-coordinate Ln-（3＋） ion, if each O,O？-chelated nitrate ligand is seen as a single coordination site, the coordination geometry can be viewed as a distorted pentagonal bipyramid. The fluorescent spectra show that compounds 2 and 3 exhibited characteristic sharp emissions of Tb-（3＋） and Sm-（3＋）, respectively, while compound 1 was found to be a single-component white-light-emitting complex in the solid state. Thermal stabilities of the three compounds were investigated by using thermal gravimetric analysis. In addition, the thermal decomposition of compound 1 was confirmed by temperature-dependent powder X-ray diffraction technique.

Ionothermal Synthesis and Fluorescence Property of a Complex Constructed by Seven Nuclear(CH_3COO)_2Co_7(OH)_2] Clusters and 4,4＇-Oxybisbenzoic Acid Ligand

A new 3D cobalt metal-organic framework [C_7H_（13）N_2]_2[（CH_3COO）_2Co_7（oba）_5-（Hoba）_2（OH）_2]·H_2O has been synthesized under ionothermal conditions and characterized by elemental analysis, FT-IR, XRD, and TG. This complex crystallizes in monoclinic system, space group P21/c with a = 19.4499（4）, b = 10.8839（2）, c = 27.7796（5） ？, β = 104.467（2）o, V = 5694.22（19） ？~3, Z = 2, C_（116）H_（92）Co_7N_4O_（42）, M_r = 2626.45, D_c = 1.532 g/cm^3 , F（000） = 2682, μ = 1.085 mm-1, R = 0.0387 and wR = 0.1177. Its structure is characterized as a 3D open framework constructed by seven nuclear clusters [（CH_3COO）_Co_7（OH）_2] and the 4,4？-oxybisbenzoic acid ligand. The used ILs cations are located in the middle of the pore and compensate for the negative charges of framework. Furthermore, its fluorescence property has also been studied.

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)3(Phen)2

A new europium（III） complex Eu（L）3（Phen）2（1） with 2-benzoylbenzoic acid（HL） and 1,10-phenanthroline（Phen） as ligands has been synthesized. Crystal data for the complex are as follows： monoclinic, space group P21/c, a = 2.2577（4）, b = 1.23484（19）, c = 1.8789（3） nm, β = 94.918（3）o, V = 5.2189（14） nm^3, Dc = 1.512 g/cm^3, Z = 4, μ（Mo Kα） = 1.269 mm^-1, F（000） = 2408, the final R = 0.0433 and w R = 0.1038. The Eu（III） ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu^3＋： ^5D0→^7F1（597 nm） and ^5D0→^7F2（615 nm） with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.

Syntheses, Crystal Structures and Luminescent Properties of Two Schiff Base Complexes

Two new transition metal complexes based on chiral Schiff base ligand, namely Zn（L_1）_2（1） and Cd（L_2）2（2）（L 1=（R,E）-3-（2-hydroxy-3-methoxybenzylideneamino）propane-1,2-diol, L2=（R,E）-2-（（2-hydroxy-1-phenylethylimino）methyl）-6-methoxyphenol）, have been synthesized and characterized. Single-crystal X-ray diffractions reveal that both 1 and 2 crystallize in the same monoclinic space group C_2. 1 is four-coordinated, while 2 is six-coordinated. Complexes 1 and 2 show fluorescent emission at 479 and 580 nm, respectively. Moreover, 1 and 2 exhibit selective and sensitive recognition toward Zn^（2＋）/Cd^（2＋） ions in the methanol solution.

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.

Synthesis, Crystal Structure and Fluorescent Property of a Zn(Ⅱ) Complex with 1,3-Bis(imidazol-1-yl)benzene and 1,3-Benzenedicarboxylate

A novel zinc complex [Zn（BIB）（bdc）]n（1, BIB = 1,3-bis（imidazol-1-yl）benzene, bdc = 1,3-benzenedicarboxylate） has been synthesized in solvothermal conditions. The title complex was characterized by elemental analysis, IR spectra, thermal analysis, single-crystal and powder X-ray diffraction. The result proved that the alliance of BIB and aromatic carboxylic acids is good for the diversity of getatable structure. Complex 1 crystallizes in the monoclinic system of P2/c space group with a = 11.5591（10）, b = 9.6239（8）, c = 33.727（3）A, β = 103.816（3）°, V = 3643.4（5） A^3, Z = 8, μ = 1.385 mm^-1, F（000） = 1792, Dc = 1.603 g/cm^3 and Mr = 439.72 g/mol. Additionally, luminescent properties of complex 1 are also investigated and it shows good fluorescence.

RARE EARTH CONTAINING POLYMER TERNARY COMPLEXES AND THEIR FLUORESCENT PROPERTIES

Rare earth containing fluorescence active polymer ternary complexes were synthesized and their absorption and emission properties were investigated.

A New Zn(Ⅱ)Coordination Polymer Constructed from 1,3,5-Benzenetricarboxylate Ligand Exhibiting Photoluminescence

The title Zn（Ⅱ） coordination polymer {[Zn2（BTC）（HBTC）（dpa）（Hdpa）]·3H2O}n（1,H3BTC = 1,3,5-benzenetricarboxylic acid,dpa = 4,4＇-dipyridylamine）,has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy and Fluorescence spectroscopy.Complex 1 belongs to the triclinic system,space group P1,a = 9.9415（4）,b = 13.5859（8）,c = 15.2987（5） A,α = 96.301（4）,β = 107.944（3）,γ = 103.575（4）°,V = 1873.48（14）A3,Z = 2,μ = 1.365 mm^-1,Dc = 1.672 g/cm^3,Mr = 943.44,F（000） = 964,the final R = 0.0314 and wR = 0.0710 with I 〉 2σ（I）.Complex 1 displays a two-dimensional bilayer coordination polymer.Complex 1 shows fluorescence in the solid state at room temperature.

Coordination Assemblies of Cd^(Ⅱ)with 5-(Ethylthio)-1H-tetrazole and Halide Ions:Synthesis,Structure,and Luminescent Properties

Three cadmium（II）-halide complexes with 5-（ethylthio）-1H-tetrazole（Hett） as ligand, namely [Cd_7Cl_2（ett）_（12）（H_2O）_2]_n（1）, [Cd_2（OH）Br（ett）_2]_n（2） and [Cd_2（OH）I（ett）_2]_n（3）, have been hydrothermally synthesized and characterized. Complex 1 was synthesized at pH = 7 and exhibits a 3D supramolecular framework, where the adjacent Cd ions form a tetrahedron unit by ett ligands bridge and the tetrahedron units share vertices to connect each other by ett bridges to form a 2D layer architecture, which is further interlinked by μ_2-Cl to form 3D structures. Complexes 2 and 3 are isostructural, generated at pH = 8.0~9.0, displaying similar 2D networks via ett ligands and different halide ions（Br-in 2, I-in 3, respectively）. In addition, thermal stabilities and luminescent properties of new complexes 1~3 have been studied.

A Linear Ce^(Ⅲ) Complex Based on in-situ Generated N-hydroxy-1,8-naphthalenedicarboximide

A Ce^(Ⅲ) linear complex of N-hydroxy-1,8-naphthalenedicarboximide(HL)has been synthesized with acenaphthoquinone dioxime(acndH_(2))under solvothermal conditions,in which L is generated by a series of in-situ reactions starting from acndH2.X-ray crystallography reveals the coordination chains of Ce^(Ⅲ) ions are assembled into a 3D supramolecular framework viaπ···πinteractions.The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis(TGA).Furthermore,the fluorescent properties study demonstrated a ligand-based emission of the Ce^(Ⅲ) complex with~6 nm blue-shift compared with the emisision of the HL ligand.

Hydrothermal syntheses and characterization of three lanthanide coordination complexes constructed by 2,2':6',2''-terpyridine and 2,2'-biphenyldicarboxylic acid

Two 1D coordination polymers [Ln2（dpdc）3（tpy）2·H2O]n [Ln=Nd 1, Yb 2, H2dpdc=2,2＇-biphenyldicarboxylic acid and tpy= 2,2＇：6＇,2＇＇-terpyridine] and one dinuclear complex Er2（dpdc）2（Hdpdc）2（tpy）2 3 were obtained via hydrothermal reactions and determined by X-ray diffraction analysis. The crystal structure data of 1 and 2 revealed that two coordination polymers were isostructural and possessed a 1D chain framework consisting of eight-coordinated Ln（III） centers. In the asymmetric unit, the two Er（III） ions in 3 were both nine-coordinated and had similar coordination environments. The Er（III） ions were bridged by dpdc2-ligands into dinuclear structures. The complexes were also characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 3 was also investigated at room temperature.

Syntheses and structures of tetranuclear Zn(Ⅱ) complexes with in situ generated macrocyclic Schiff base ligands:Applications in Zn^(2+) sensing

Three novel Zn（II） complexes,[Zn4L1Cl4]-3H2O（1）,[Zn4L2Cl4]-2DMF（2） and[Zn4L^3Cl4]H2O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ＇2 ＋ 2＇ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn^2＋ sensors have been investigated.Take H4L^1 for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn^2＋ in MeOH.

Heterometal–organic frameworks: Three novel copper(Ⅱ)–lanthanide(Ⅲ) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform

Reactions of copper（Ⅱ） sulfate or copper（Ⅱ） perchlorate,samarium（Ⅲ）,erbium（Ⅲ） or neodymium（Ⅲ）nitrate（5/1 equiv.） with pyrazinohydroxamic acid（H2Pyzha） in H2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis：metallacrown[Sm（H2O）3 {Cu（pyzha）}5（H2O）2（MeOH）（HSO4）2]·（H2O）2（HSO4）（1）;[Nd（H2O）2（MeOH） {Cu（pyzha）}5（ClO4）2（H2O）5（NO3）]（2）;[Eu（H2O）2（MeOH） {Cu（pyzha）}5（ClO4）2（H2O）5（NO3）]（3）.The differentiation of atomic and ionic radii between the encapsulated lanthanide（Ⅲ） could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium（Ⅲ）,while 2and 3 show that of copper（Ⅱ） and ligand.

Synthesis,crystal structures and complexing ability of difunctionalized copillar[5]arene Schiff bases

An efficient method for the synthesis of some difunctionalized copillar[5]arene Schiff bases from condensation of salicylaldehyde and its 5-chloro,5-bromo,3,5-di（t-butyl） substituted derivatives with corresponding diamino-functionalized copillar[5]arene,which were prepared by Gabriel reaction according to the reported method.Single-crystals of six copillar[5]arenes were determined by X-ray diffraction.An ORTEP of compounds showed that the two chains units of Schiff base exist in the outside of the cavity of pillar[5]arene.Furthermore,the complexing ability of these Schiff bases to transition metal ions were investigated by UV and fluorescence spectroscopy.