两个基于4-(1H-1,2,4-三氮唑)苯甲酸的稀土配位聚合物的合成、晶体结构及荧光性质(英文)

以4-(1H-1,2,4-三氮唑)苯甲酸为配体,采用水热法合成了2种稀土配位聚合物[Tb(tbc3)(H2O)3]n(1)和{[Nd(tbc3)(H2O)3]·H2O}n(2)(Htbc=4-(1H-1,2,4-三氮唑)苯甲酸)。运用X-射线单晶衍射法对该配位聚合物进行了结构测定,并对其进行了元素分析、红外光谱、TG及荧光光谱表征。单晶结构表明,配位聚合物1为三斜晶系,空间群P1,配位聚合物2属于单斜晶系,空间群为P21/c。配位聚合物1和2均为一维链结构,均通过非共价键作用形成三维超分子构造。     

基于3,3′,5,5′-(1,3-苯基)-联苯四羧酸构筑的两个配位聚合物的合成、晶体结构和荧光性质(英文)

以3,3′,5,5′-(1,3-苯基)-联苯四羧酸(H4btb)与1,10-菲咯啉(phen)为配体,分别与硝酸镉和硝酸锌在水热条件下反应合成2个一维[Cd(H2btb)(phen)]n(1)和二维{[Zn2(btb)(phen)]·1.5H2O}n(2)配位聚合物,并对其进行了元素分析、红外光谱、热重分析和X-射线单晶衍射测定。配合物1属于单斜晶系,空间群为C2/c,晶胞参数:a=2.82845(13)nm,b=1.08554(5)nm,c=1.81768(8)nm,β=96.4850(10)°,V=5.5453(4)nm3,Z=8,Dc=1.670Mg·m-3,F(000)=2800,R1=0.0339,wR2=0.0718[I2σ(I)],配体H4btb的2个羧基分别采取μ1-η1∶η1、μ2-η2∶η1配位模式连接镉原子形成一维带状结构。化合物2也属于单斜晶系,空间群为P21/c,晶胞参数:a=1.7471(3)nm,b=1.2511(2)nm,c=2.1870(3)nm,β=120.911(11)°,V=4.1014(11)nm3,Z=4,Dc=1.491Mg·m-3,F(000)=1876,R1=0.0673,wR2=0.1749[I2σ(I)],全部去质子的H4btb配体的4个羧基分别采取μ1-η1∶η0、μ1-η1∶η1、μ2-η1∶η1配位模式连接锌原子形成一维链,链间通过μ2-η1∶η1桥连羧基扩展为(3,5)-连接的二维(42·67·8)(42·6)网状结构。同时研究了2个配合物的荧光性质。     

Ag~+型配位树脂的制备及对FK506分离纯化的研究

将HZM-3大孔树脂磺化,动态法载银依次获得Ag+-1#、Ag+-2#、Ag+-3#、Ag+-4#、Ag+-5#共5种Ag+型配位树脂,通过它们对FK506的静态吸附与解吸实验优选出了Ag+-3#树脂,其吸附率为77%,解吸率为92%;Ag+-3#树脂与FK506形成络合物的稳定性受溶液极性的影响,在室温下的静态吸附曲线表明,其对FK506的配位吸附符合Langmuir单分子层吸附模型;Ag+-3#树脂配位层析分离FK506,当甲醇:乙酸乙酯(V/V)=50:50,上样量为8mg/m L,流速为1BV/h时,可在4.5倍柱体积内完成整个分离过程,合并不含类似物的收集液,浓缩后在HPLC上检测纯度为98.83%,收率为87.35%,无类似物FK520与2H-FK506检出;乙醇结晶最终产品的纯度达到99.6%以上,样品经过ICP-AES检测,在其检测限内未检测出Ag+。     

The effects of surface ligands and counter cations on the stability of anionic thiolated M12Ag32 （M=Au,Ag） nanoclusters

The stabilities of [M12Ag32（SR）30]4- （M = Ag, Au and SR = SPhF2, SPhCF3, SPhF） clusters having the same structure but different surface ligands or counter cations were systematically studied. It was clearly revealed that a subtle structural change in the surface ligands or counter cations could significantly alter the overall stability of [M12Ag32（SR）30]4 although they all had an electronic structure of 18-electron superatom shell closure. SPhF2 was found as a better surface ligand than SPhCF3 or SPhF to stabilize [M12Ag32（SR）30]4-. And the use of more bulky [（PPhj）2N]＋ as the counter cations was revealed to be more deleterious to the overall stability of [M12Ag32（SR）30]4- clusters than PPh4＋. [Au12Ag32（SR）30]4- was much more stable than [Ag44（SR）30]4 with the same surface ligands and counter cations. An exceptional stability was observed on （PPh4）4[Au12Ag32（SPhF2）30] which was stable in DMF for more than 8 days in air at 80 ℃. More research efforts are still needed to deeply understand why a small structural change could result in a significant change in the stability of noble metal nanoclusters.     

双烯烃配位链转移聚合研究进展

可逆配位链转移催化体系由过渡金属催化剂和主族金属烷基化合物组成,聚合物链在两者间进行快速可逆的链转移反应实现了聚合物的分子量、分子量分布的可控,且能够得到具有不同拓扑结构及立体选择性的均聚物和共聚物。配位链转移聚合(CCTP)除具有传统的活性阴离子聚合的优点之外,更重要的是,其平均每个活性中心可产生多条聚合物链,中心金属利用率超过100%,且催化剂立体选择性强。本文简要介绍了双烯烃配位链转移聚合研究进展,包括CCTP的基本原理,双烯烃配位链转移均聚合、共聚合及链穿梭聚合方面的研究。     

A New Terbium（III） Coordination Compound with 2-Thiophenecarboxylic Ligand： Synthesis and Crystal Structure①

A new coordination compound with formula [Tb（2-TC）3（DMF）]n （1, 2-TC = 2-thio- phenecarboxylic ligand and DMF = dimethylformamide） was synthesized by solvothermal method. The structure of compound 1 was determined by single-crystal X-ray diffraction analyses, and characterized by elemental analyses, IR and powder X-ray diffraction. Structure analysis reveals compound 1, exhibiting a one-dimensional chain structure, crystallizes in triclinic space group P21/c, with a = 9.2751（19）, b = 16.490（3）, c = 15.865（5） A, β = 118.98（2）°, V= 2122.7（9）A3, D,. = 1.916 g/cm3, Mr= 612.45 （C18H15NO7S3Tb）, F（000） = 1196,μ（MoKa） = 3.67 mm-1, Z = 4, R = 0.0616 and wR = 0.0962 for 3865 observed reflections （I 〉 2o（I））, and R = 0.1092 for all data. Meanwhile, the photoluminescent properties of compound 1 were also investigated in the solid state at room temperature.     

A New Cadmium（II） Coordination Polymer Constructed by 2-（2-Chloro-6-fluorophenyl）-lH-imidazo[4,5-f] [1, 10]phenanthroline and 1,2,3-Benzenecarboxylate： Synthesis,Structure and Luminescence

A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650（2）, b = 12.240（2）, c = 19.760（4） A, α = 72.01（3）, β = 77.11（3）, γ = 83.48（3）°, V = 2609.4（9） A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F（000） = 1466, μ（MoKa） = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.     

Recent Advances of Lanthanide-transition Heterometallic Coordination Polymers

With the improvement of high-tech and emergence of crossing and new fields,lanthanide-transition(Ln–M) heterometallic coordination polymers have attracted much attention of many researchers,which exhibit novel structures and unique properties with potential applications in the nonlinear optical materials,fluorescent materials,superconducting materials,magnetic materials,catalysis,bio-simulation,adsorption and separation,and so on.It is thus necessary to summarize Ln–M heterometallic coordination polymers.According to the transition metal ions,those coordination polymers are divided into six parts to explore the current applications and future developments.     

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {（NH4）2[Cd（H20）Fe（CN）6]}n： Synthesis and Crystal Structure①

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.     

Synthesis,Structure and Magnetic Property of One Ni~Ⅱ Based Coordination Polymer

One new coordination polymer, [Ni(m-bix)(m-BDC)](1, m-bix = 1,3-bis(imidazol-1-ylmethyl)benzene, m-BDC = 1,3-benzenedicarboxylic acids), has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The green block crystal of complex 1(C22H18N4Ni O4) belongs to monoclinic system, space group P21/c with a = 10.0418(3), b = 23.8651(6), c = 8.7872(2) A, β = 112.333(3)o, V = 1947.88(9)A3, Z = 4, Dc = 1.572 g/cm3, Mr = 461.11, F(000) = 952, R = 0.0335 and w R = 0.0683 for 2827 observed reflections(I 2σ(I)). Complex 1 exhibits a novel 6-connected 3D sxd type topological framework. The magnetic characterization of complex 1 shows antiferromagnetic coupling exchange.