吡唑-3-甲酸Cu(Ⅱ)/Mn(Ⅱ)配合物的合成、表征及常压下对二氧化碳催化转化

合成和表征了2个吡唑-3-甲酸过渡金属配合物[Cu₂（pca）₂（H₂O）₆]·2H₂O（1）,[Mn（Hpca）₂（phen）]·3H₂O（2）（H₂pca=吡唑-3-甲酸;phen=菲咯啉）。X射线单晶衍射分析结果表明,配合物1属于单斜晶系P2₁/n空间群,它是一个畸变八面体的双核铜配合物;配合物2是一个畸变八面体的单核锰配合物。配合物1和2分别通过分子间的O-H…O,N-H…O氢键形成了三维网状结构。配合物1在二氧化碳的环加成反应中显示出了良好的催化效率（转化率高达97.4%;选择性高达98.9%）。     

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)₂(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H₂DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^o,V=4056.6(16)A³,Z=4,C₄₅H₂₂Cl₂F₂Mn N₁₀O₇,M_r=978.57,D_c=1.602 g/cm³,F(000)=1980,μ(Mo Ka)=0.536 mm^–1,R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^o,V=4742.0(12)A³,Z=8,C₂₇H₁₄Cl Co FN₄O₄,M_r=517.80,D_c=1.602 g/cm³,F(000)=2312,μ(Mo Ka)=0.889 mm^–1,R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.     

一种不对称Salamo-型螯合配体及其钴髤配合物：合成、表征与晶体结构

合成了一种不对称Salamo-型螯合配体4-氯-6′-甲氧基-2,2′-[乙二氧双(氮次甲基)]二酚(H2L)及其钴髤配合物[Co(L)(H2O)],并通过元素分析、红外光谱、紫外-可见吸收光谱及X-射线单晶衍射方法对配体H2L及其配合物进行了表征。结果表明:配体属单斜晶系,P21/n空间群,配合物属正交晶系,Iba2空间群。配合物为单核结构,由1个Co髤离子和1个四齿的L2-配体单元和1个配位水分子组成,中心Co髤原子的配位数是5,且具有稍微扭曲的三角双锥几何结构,而配合物分子通过分子间C8-H8···Cl1氢键组装成1D链状的超分子结构。     

A series of Wells-Dawson and Keggin-based compounds with uncoordinated S donors as fluorescence sensors to Hg2+

Abstract

Through using a S-containing ligand 2,2’-dimethyl-4,4’-bithiazole (dbt), a series of Wells-Dawson and Keggin-based compounds, {Zn(dbt)₃}{Zn(dbt)₂(H₂O)}₂{HP₂W^VW^VI₁₇O₆₂}·4H₂O (1), {Cd(dbt)₂(H₂O) (HP₂W^VW^VI₁₇O₆₂)}{Cd(dbt)₃}{Cd(dbt)₂(H₂O)}·13H₂O (2), {Cd₂(dbt)₄Cl} {PW₁₂O₄₀} (3) and {Cd₂(dbt)₄}{SiW₁₂O₄₀} (4), were synthesized under hydrothermal conditions and structurally characterized. In 1, there are three dissociated subunits: Wells-Dawson anion, {Zn(dbt)₃}²⁺ and {Zn(dbt)₂(H₂O)}²⁺. In 2, the mono-supporting Wells-Dawson anions exhibit abundant hydrogen bonding interactions with discrete {Cd(dbt)₃}²⁺ and {Cd(dbt)₂(H₂O)}²⁺ mononuclear coordination complexes, constructing a supramolecular layer. Compound 3 has a binuclear Cd cluster {Cd₂(dbt)₄Cl}⁴⁺ with a Cl as a bridging atom. The Keggin anions link these binuclear Cd clusters alternately to build a 1D chain. In 4, a pair of {Cd(dbt)₂}²⁺ subunits connect adjacent Keggin anions and a 1D chain is formed. In these four compounds, only the N donors coordinate with Zn or Cd and the S atoms are uncoordinated. These compounds show good fluorescence sensing performance to Hg²⁺. We also studied the electrochemical and photocatalytic properties of 1–4. These compounds also can act as electrochemical sensors for the detection of nitrite.     

Salamo型三核镍(Ⅱ)配合物的合成、晶体结构与Hirshfeld表面分析

合成了2种新设计的Salamo型配合物,{[Ni（L¹）（n-propanol）]₂（OAc）₂Ni}·2（n-propanol）（1）和{[Ni（L²）（n-butanol）]₂（OAc）₂Ni}·2（n-butanol）（2）,并用元素分析、红外光谱、紫外-可见光谱、Hirshfeld表面分析和单晶X射线晶体学对其进行了表征。X射线晶体学分析表明,配合物1和2均为对称的三核镍（Ⅱ）配合物。1和2中的镍（Ⅱ）都是六配位的,形成了扭曲的八面体几何构型。晶体结构分析和Hirshfeld表面分析均表明,1和2通过分子间氢键作用分别形成稳定的一维链状和二维超分子结构。     

金纳米粒子与单链DNA的相互作用

研究了金纳米粒子与单链DNA在不同pH值时的相互作用以及金纳米粒子与不同碱基序列单链DNA的相互作用. 结果表明, 在pH为12.6的强碱性条件下, 单链DNA能使金纳米粒子稳定分散在溶液中; 在pH为1.4的强酸性条件下, 单链DNA能保护金纳米粒子不发生融合, 而只发生团聚, 且团聚现象具有可逆性. 不同寡核苷酸对金纳米粒子的亲和力按poly dA>poly dC>poly dT的顺序依次减弱. 单链DNA对纳米金的保护作用强度与单链DNA的长度成正比.     

Facile One-Pot Method for the Synthesis of Polysubstituted Phthalide Derivatives

A new three-component cyclization method is described involving two starting materials, ethyl 4-chloroacetoacetate and aldehydes, catalyzed by piperidine, acid, and iodine. Ten corresponding polysubstituted phthalides are formed with good yields (44–78%). A mechanism of the reaction is also proposed.     

First-Principles Study on the Electronic Structures for Y^3＋：PbWO4 Crystals

The possible defect models of Y^3＋：PbWO4 crystals are discussed by defect chemistry and the most possible substituting positions of the impurity Y^3＋ ions are studied by using the general utility lattice program （GULP）. The calculated results indicate that in the lightly doped Y^3＋ ：PWO crystal, the main compensating mechanism is [2Ypb^＋ ＋ VPb^2-], and in the heavily doped Y^3＋ ：PWO crystal, it will bring interstitial oxygen ions to compensate the positive electricity caused by YPb^＋, forming defect clusters of [2Ypb^＋ ＋Oi^2-] in the crystal. The electronic structures of Y3＋ ：PWO with different defect models are calculated using the DV-Xα method. It can be concluded from the electronic structures that, for lightly doped cases, the energy gap of the crystal would be broadened and the 420nm absorption band will be restricted; for heavily doped cases, because of the existence of interstitial oxygen ions, it can bring a new absorption band and reduce the radiation hardness of the crystal.     

μ-氧代四苯基双核金属卟啉仿生催化剂的研究进展

综述了国内外及本课题组有关μ-氧代四苯基双核金属卟啉仿生催化剂合成及应用的最新研究进展和成果. 重点介绍了μ-氧代四苯基双核金属卟啉的合成方法, 即两步合成法、柱色谱分离法、一步合成法、自氧化法以及本课题组最新开发的一锅法. 其中一步合成法和自氧化法由于具有适用范围广、收率高等优点, 将成为μ-氧代四苯基双核金属卟啉的主要合成方法. 而一锅法尽管目前收率尚较低, 但由于其完全去掉了中间反应产物的分离和提纯以及原料和溶剂的损失, 而使工艺流程得到大大简化、能耗显著降低, 将成为一种极有发展潜力的合成方法. 系统地阐述了μ-氧代四苯基双核金属卟啉在仿生催化领域中的应用. 尤其是以μ-氧代四苯基双核金属卟啉为催化剂、O2或空气为氧化剂的催化氧化反应, 具有催化剂用量少、氧化剂清洁且廉价易得、无需助催化剂和共还原剂、反应条件温和等优点, 将成为未来仿生催化氧化领域研究的前沿和热点.     

基于咪唑羧酸配体镉(Ⅱ)配合物的合成、结构调控及其性质表征

利用水热法，以2-（4-羧基-苯基）咪唑-4，5-二羧酸（H₃L）为主配体，在辅配体1，10-菲咯啉（1，10-phen）和1，4-二（1-咪唑基）苯（dib）的调控作用下得到2个新的镉（Ⅱ）配合物：[Cd₂（HL）₂（1，10-phen）₂（H₂O）₂]（1），{[Cd （HL）（dib）_0.5（H₂O）₂]·2H₂O}_n（2）。并通过单晶X射线衍射、元素分析、热重分析、粉末X射线衍射、红外光谱、Hirshfeld表面分析和密度泛函理论量化计算对1和2进行了分析和表征。配合物1和2均属于三斜晶系和P1空间群，且1为零维结构，2为一维链状结构。