Syntheses,Crystal Structures and Luminescent Properties of Two Lanthanide Coordination Polymers Based on Bifunctional Ligand

Two lanthanide coordination polymers, [Eu（HL）（L）（H2O）2]n（1） and [Tb（H0.5L）2]n（2）, based on bifunctional 5-（1H-imidazol-1-yl） isophthalic acid（H2L）, are hydrothermally synthesized and characterized by both single-crystal and powder X-ray diffraction analyses, and FT-IR. In compound 1, the basic inorganic building unit of the coordination network is the dinuclear [Eu2（COO）6] cluster. Each [Eu2（COO）6] cluster connects four HL^- ligands and each HLligand links two [Eu2（COO）6] clusters, resulting in a 2D coordination layer. The adjacent 2 D layers are further connected via neighboring inter-layer hydrogen bonds to give a 3D supramolecular structure. In compound 2, the Tb^3＋ is coordinated to six oxygen atoms. Each Tb^3＋ ion connects six ligands and each ligand links three Tb^3＋ ions, leading to a 3D coordination polymeric network which exhibits remarkably high thermal stability up to 500℃. Furthermore, due to the successful incorporation of Tb^3＋, compound 2 displays characteristic luminescent emission in the solid state at room temperature. The combination of high thermal stability and fluorescent property of compound 2 would make it as a promising light-emitting material.

Mononuclear and Dinuclear Yttrium Complexes Supported by Pyrrolide Ligands： Syntheses, Structures and Catalytic Behaviors towards the Ring-opening Polymerization of ε-Caprolactone

The syntheses, structures and catalytic activities of two yttrium complexes supported by pyrrolide ligands are reported. Treatment of Y（N（Si Me3）2）3 with one equivalent of H3bptd（H3bptd = 1,9-bis（2-pyrrolyl）-2,5,8-triazanona-1,8-diene） in THF gave a complex of composition [Y（bptd）（THF）]2（1）. Reaction of Y（N（Si Me3）2）3 with one equivalent of H3tpa（H3tpa = tris（pyrrolyl-α-methyl）amine） in THF generated [Y（tpa）（THF）3]（2） in good yield. Complexes 1and 2 have been characterized by single-crystal X-ray diffraction, elemental analyses and NMR spectroscopy. Complex 1 is dinuclear. The two metal centers are doubly bridged by two amine nitrogen atoms to form a Y–N–Y–N four-membered rhombus ring. The geometries of Y^3＋ ions in 1and 2 are well described as pentagonal bipyramid and capped octahedron, respectively. The ring-opening polymerization reactions of ε-caprolactone initiated by 1 and 2, respectively, were investigated. They both exhibited good catalytic activity for the polymerization of ε-caprolactone. All of the obtained polymers have high molecular weights and relatively narrower PDIs. The polymers generated by 2 possessed polydispersity close to 1.1. The good catalytic activities of 1 and 2 reveal their potential applications in polymer industry.

A Pair of 3D Homochiral Coordination Polymers with Open Channels Constructed by Lactic Acid Derivative Ligands and In-situ Formed Anions

With the help of in-situ formed CH_3COO- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd（II） ions, namely [Cd3（（R）-CIA）2（CH3CO2）_2（1.4-DIB）2（H2O）2]·x（Guest）（1-D） and [Cd3（（S）-CIA）2（CH3CO2）2（1.4-DIB）2（H2O）2]·x（Guest）（1-L）. They contain 1D interesting ladder-like Cd-（R）-CIA（3-） chains and exhibit SHG-active behavior and photoluminescent property.

SYNTHESIS OF ORGANOGERMANE OLIGOMERS VIA LIGAND SUBSTITUTION POLYMERIZATION FROM 1, 4-DIOXANE COMPLEX OF GERMANIUM DICHLORIDE

Some organogermanium oligomers with different side groups were synthesized via ligand substitution polymerization from I, l-dioxane complex of germanium dichloride with different organolithium compounds. The oligomers were isolated through either precipitation from methanol or extraction using toluene with a yield of no less than 50%. The weight average molecular weight (M-w) of the oligomers is ranging from 1.4 x 10(3) to 5.9 x 10(3) depending on the type and alkyl length of the organolithium compounds used.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

POLYMERIZATION OF METHYL METHACRYLATE CHIRAL LIGANDS

Methyl methacrylate was anionically polymerized in the presence of chiral ligands, e. g. (+)-DDB and (-)-Sp. The polymers thus formed were optically inactive due to the instability of the helical chain for the less bulky ester group. Isotactic poly(methyl methacrylate) was given when (+)-DDB was used, whereas, a syndiotactic polymer was formed in the presence of (-)-Sp. Accordingly, two different propagation mechanisms were postulated.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [（IP）（H2SO4）（H2O）]（1）, [（H2SDC）（BPA）]（2） and [Mn（SDC）（IP）2]n （3）, have been constructed by three modes（rigid IP, rigid SDC ＋ flexible BPA, rigid IP ＋ rigid SDC）. Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.

Synthesis and Characterization of a Palladium Complex Supported by Bidentate Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{[2-[（2,4-dimethylphenyl）imino]-5-methoxyl]-phenol}-palladium（Ⅱ）（CC_（32）H_（32）N_2O_4Pd） has been synthesized by the reaction of 2-[（2,4-dimethylphenyl）imino]-5-methoxyl-phenol with Pd（CH_3COO）_2,and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P2_1/c with a = 12.058（2）,b = 8.3624（17）,c = 14.735（3） ？,β = 107.66（3）°,V = 1415.7（5）？~3,C_（32）H_（32）N_2O_4Pd,Mr = 615,Z = 2,D_c = 1.443 Mg/m^3,μ = 0.695 mm^（-1）,F（000） = 632,T = 293（2） K,the final R = 0.0514 and w R = 0.1356（I 〉 2s（I））.Under the co-catalysis of methylaluminoxane（MAO）,the palladium compound exhibited favorable catalytic activity for the polymerization of norbornene（NB）.

Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]n（1,H2L1 = 5-（4-pyridyl）-methoxyl isophthalic acid） and[Ni（L2）2（H2O）4]n（2,HL2 = 4-（pyridin-4-ylmethoxy）benzolic acid）,have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1^2- anions connecting the Zn2（O2C）4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2^- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional（3D） supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

Syntheses,Crystal Structures and Luminescent Properties of Two New Zinc(Ⅱ) Complexes Based on Bifunctional Ligand

By using solvothermal method,two novel coordination polymers based on 4-（4-carboxyphen-yl）-1,2,4-triazole（Hcpt） and Zn（Ⅱ） cations,[Zn（cpt）（OH）]_n·n H_2O（FJU-32） and [Zn（cpt）（atrz）]n（FJU-33）（Hatrz = 3-amino-1,2,4-triazolate）,were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441（3）,b = 23.0384（19）,c = 11.8562（10） ？,β = 99.069（8）o,V = 1009.91（15） ？3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F（000） = 916,μ（MoKα） = 2.439 mm^（-1）,Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections（I 〉 2σ（I））,and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483（5）,b = 9.9922（3）,c = 9.8403（3） ？,β = 100.756（4）°,V = 1231.47（7） ？~3,Dc = 1.816 g/cm^3,C_（11）H_9N_7O_2Zn,Mr = 336.62,F（000） = 680,μ（Cu Kα） = 2.957 mm^（-1）,Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections（I 〉 2σ（I））,and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn（Ⅱ） is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn（atrz）] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.

Zinc Complexes of New Chiral Aminophenolate Ligands: Synthesis, Characterization and Reactivity toward Lactide

The syntheses of a library of new chiral aminophenolate bidentate O,N-type ligands HOC6H4(2-R- 4-R′)CH2N(Me)CH(Me)C6H5 [R = R′ = But, 1;R = R′ = Pent, 2;R = But, R′ = Me, 3;R = Me, R′ = But, 4;R = R′ = Me, 5] and tridentate O,N,O-type ligands HOC6H4(2,4-But)CH = NCH(R′′)C6H5 [R′′ = Me, 6;R′′ = CH2OMe, 7] are reported. These ligands were characterized by elemental analysis, nuclear magnetic resonance spectroscopy (1H & 13C), and single crystal X-ray diffraction. These ligands serve as chiral auxiliaries for inorganic chemists to design chiral metal-based complexes for asymmetric catalysis and stereoselective polymerization reactions. Three new heteroleptic zinc complexes based on these ligands have been synthesized in moderate yields via a ligand-exchange transamination reaction between homoleptic [Zn(N(SiMe3)2)2] and one equivalent of corresponding ligands to afford [L3ZnN- (SiMe3)2] (3a), [L4ZnN(SiMe3)2] (4a), and [L7ZnN(SiMe3)2] (7a). Solvent-free polymerization of raclactide at 130°C using these zinc compounds yielded atactic polylactides with Mw 10,000 g/mol and narrow polydispersity of 1.3.

Synthesis and Characterization of New Chiral Monoanionic [ON] Ancillary Phenolate Ligands

Three new chiral monoanionic [ON] ancillary phenolate ligands with varying pendant arms have been synthesized in moderate to high yields (50% - 85%) via Mannich-type condensation reaction of chiral substituted phenol, formaldehyde and (+)-bis-[(R)-1-phenylethyl]amine. These new organic compounds were fully characterized via nuclear magnetic resonance spectroscopy (1H and 13C) and elemental analysis. The newly synthesized ligands are suitable candidates for metal-catalyzed ring-opening of lactones and asymmetric catalysis.

Iron(III)-Mediated AGET ATRP of Methyl Methacrylate in the Absence of Additional Ligand

The atom transfer radical polymerization on the mechanism of activator generation by electron transfer (AGET ATRP) of methyl methacrylate (MMA) in N,N-dimethylformamide (DMF) in the presence of the catalytic systems, namely, CCl4-FeCl3-1-acetyl-2-phenylhydrazine (APH) and CCl4-FeCl3-ascorbic acid (AA) is reported. The living feature of this process was confirmed by obtaining well-defined polymers with controlled molecular weight, narrow molecular weight distribution, and a chain-extension experiment. Both reducing agents, an APH as well as an AA, possess the equal kinetic activitis.

双β-二酮钛系烯烃聚合催化剂的合成、表征及其催化乙烯聚合

合成了一种新型β-二酮钛配合物[(acac)_(2)Ti(C_(6)H_(6))_(2)(3a)、(acac)_(2)Ti(C_(6)H_(5)OCH_(3))_(2)(3b)、(acac)_(2)Ti(C_(6)H_(5)CF_(3))_(2)(3c)],采用^(1)H NMR、^(13)C NMR、元素分析等方法进行表征。用配合物作催化剂,以甲基铝氧烷(MAO)为助催化剂催化乙烯聚合,研究了聚合条件(如Al/Ti摩尔比、聚合温度和催化剂结构)对催化活性的影响。其中3a对乙烯聚合活性达6.26×10^(5)g·mol^(-1)·h^(-1),聚合物最大的重均分子量M_(w)为13.47 kg·mol^(-1),分子量分布PDI为2.0。

蒽基取代含酚单茂催化剂在乙烯聚合中的应用

以蒽基取代的含酚单茂催化剂为主催化剂,三苯甲基四(五氟苯基)硼酸盐为助催化剂进行了乙烯均聚和乙烯/α-烯烃共聚反应,利用DSC,GPC等方法考察了该催化体系在不同聚合条件下的聚合性能。实验结果表明,该催化体系催化乙烯均聚的活性最高可达到3.36×10^(6)g/(mol·h)。适宜的聚合条件为:催化剂用量10μmol,n(Al)∶n(Ti)=150,n(B)∶n(Ti)=1.5,反应温度20℃,反应压力0.4 MPa,聚合时间10 min,液体总体积200 mL。在该条件下还可催化乙烯与α-烯烃共聚,其中,与1-辛烯共聚时,聚合活性最高可达2.00×10^(6)g/(mol·h),共聚物密度在0.859~0.876 g/cm3之间,玻璃化转变温度均低于-52℃,符合乙烯共聚弹性体的结构性能特征,且通过调节共聚单体浓度能有效控制乙烯共聚物链结构。

钴系催化剂催化共轭二烯烃聚合研究进展

综述了钴系催化剂在共轭二烯烃聚合领域的发展,详细总结了使用不同种类钴催化体系和含不同类型配体的钴配合物催化丁二烯、异戊二烯等共轭二烯烃聚合的催化活性和对聚合物微观结构(区域规整度、顺式-1,4-结构、反式-1,4-结构、1,2-结构和3,4-结构)及其立构规整度(间规度、等规度、微观结构序列分布)、聚合物分子量及其分布等的影响,展望了钴系催化剂在催化共轭二烯烃聚合方面的研究方向。

新型络合吸附剂的研究(Ⅱ)——铜离子模板高分子多乙烯多胺络合吸附剂的合成和特性

以金属Cu(Ⅱ)离子为模板,合成了高分子多乙烯多胺络合吸附剂,研究了它们对重金属离子(Cu^(2+),Ni^(2+),Co^(2+),Zn^(2+))的吸附特性。发现这类吸附剂具有高吸附容量和优良的吸附选择性。