Zn(Thr)Ac2•2H2O固态配合物的制备及标准生成焓

在水-丙酮混合溶剂中合成了未见文献报导的Zn(Thr)Ac2•2H2O固态配合物,通过化学分析、元素分析、IR、XRD和TG-DTG等对其组成、结构及热稳定性进行了研究.用微量热法测定了配合物在298.15 K时在纯水中的溶解焓,计算了Zn(Thr)2＋(aq,∞)和Zn(Thr)Ac2•2H2O(s) 的标准摩尔生成焓分别为(955.24±5.70) kJ•mol－1和(-570.92±5.71) kJ•mol－1.     

两种3D微孔Zn-MOF对水溶液中Fe3+、Cr2O72-和丙酮分子的荧光传感(英文)

通过溶剂热法合成了2种三维微孔锌金属有机框架材料,其分子式为[Zn₃(DBA)(OH)(1,10-phen)₂]_n (1)和{[Zn₂(HDBA)(4,4′-bipy)_1.5]·H₂O}_n (2)(H₅DBA=3,5-二(2′,4′-对羧基苯基)苯甲酸;1,10-phen=1,10-菲咯啉;4,4′-bipy=4,4′-联吡啶)。结构分析表明,配合物1为三核锌基金属单元的三维微孔骨架,配合物2为双核锌基的微孔结构。与2相比,配合物1在水中具有较强的发光性能,可作为检测Fe³⁺、Cr₂O₇^2-和丙酮分子的发光传感器,具有较高的选择性和灵敏度。     

水合氯化镧与二乙氨基荒酸二乙铵配合行为的热化学

在干燥氮气气氛下，以无水乙醇为溶剂，制备了低水合氯化镧与二乙氨基荒酸 二乙铵（D-DDC）的配合物，确定其组成为Et_2NH_2[La(S_2CNEt_2)_4]。用微量热 法测定了298.15 K下水合氯化镧和D-DDC在无水乙醇中的溶解焓和不同温度下二乙 氨基荒酸镧液相生成反应的焓变。在实验和计算基础上，得到了液相生成反应的热 力学参数（活化焓、活化熵和活化自由能）、速率常数和动力学参数（表现活化能 、频率因子和反应基数），通过合理的热化学循环，求得了标题固相反应的焓变。     

Two New Silver Coordination Polymers Constructed from 3,3-Azodibenzoic Acid and Different Pyridine Derivatives:Syntheses,Structures and Fluorescent Properties

Two coordination polymers(CPs),{[Ag(ADA)_(0.5)(DPE)]·H_2O}_n(1) and {[Ag(ADA)_(0.5)(Bipy)_(0.5)]·H_2O}_n(2),(H_2ADA = 3,3-azodibenzoic acid,DPE = 1,2-di(4-pyridyl)-ethylene,Bipy = 4,4?-bipyridine),have been synthesized via solvothermal reactions of Ag+ with ADA~(2-) and/or DPE,Bipy.CPs 1 and 2 were characterized by elemental analyses,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.CPs 1 and 2 feature "Ag···Ag" subunits.CP 1 shows a 3D construction,in which the "Ag···Ag" subunits extend through ADA~(2-) and DPE ligands using μ6-kO,O;kO;kO;kO,O;kO;kO and μ_2-kO;kO coordination modes,respectively.It crystallizes in triclinic system,space group P1,with a = 0.3808(18),b = 1.2476(6),c = 1.309(6) nm,α = 76.757(5),β = 84.649(5),γ = 86.809(5)o,V = 0.6024(5) nm~3,Z = 2,Mr = 351.11,C_(13)H_(11)AgN_2O_3,Dc = 1.936 g/cm3,F(000) = 348,S = 1.064,R = 0.0323 and w R = 0.0689.CP 2 exhibits a 3 D supramolecular structure,in which the "Ag···Ag" subunits are connected by ADA~(2-) and DPE ligands with μ_6-kO;kO;kO,O;kO;kO and μ_2-kO;kO coordination modes,respectively.Ultimately,through hydrogen bond and π???π interaction,the "Ag···Ag" subunits stabilize the 3D supramolecular structure of 2.It crystallizes in monoclinic,space group C2/c,with a = 25.301(15),b = 13.197(8),c = 6.970(4) nm,β = 102.597(7)o,V = 2.271(2) nm~3,Z = 8,C_(12)H_(10)AgN_2O_(2.50),M_r = 330.09,D_c = 1.931 g/cm~3,F(000) = 1304,S = 1.082,R = 0.1107 and wR = 0.2984.The fluorescence properties of CPs 1 and 2 have been also investigated.     

间苯二乙酸构筑的2D锰(Ⅱ)配合物的合成及晶体结构

利用柔性配体合成了配合物[Mn(pda)(bpp)](1)(H2pda=1,3-phenylenediacetic acid,bpp=1,3-bi(4-pyridyl)propane),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于正交晶系,空间群为Pnna,a=1.965 2(6)nm,b=1.103 3(4)nm,c=0.963 9(3)nm,α=β=γ=90.0°,V=2.089 8(12)nm3,Z=4,Dc=1.416 Mg.m-3,μ=0.664 mm-1,F(000)=924,R1=0.040 2,wR2=0.133 2(I>2σ(I))。配合物1的结构单元由1个MnⅡ、1个1,3-pda和1个bpp构成。bpp交替连接MnⅡ形成1D右手螺旋链,进一步通过1,3-pda的连接构成2D螺旋层。从c轴方向看,发现1DZ字链构成2D(4,4)网格结构。同时还研究了配合物的热稳定性和电化学性质。     

四种同构镧系金属有机框架的合成、结构和荧光传感Fe3+和盐酸环丙沙星

采用溶剂热法,以含氮四羧酸3,5-二(3′,5′-二羧苯)-1H-1,2,4-三唑(H₄BDT)为配体,成功合成了4种同构镧系金属有机框架(Ln-MOFs)：{[La₃(BDT)₂(HCOO)(H₂O)₅]·0.5H₂O·3DMF}_n (1)、{[Ce₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (2)、{[Pr₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (3)和{[Nd₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n (4),并采用单晶X射线衍射、粉末X射线衍射、元素分析、热重、红外、N₂吸附实验和荧光光谱对其进行表征。结果表明,这些Ln-MOFs均为单斜C2/m空间群晶体,是双核为无机建筑单元的三维介孔结构。其中2可选择性荧光检测Fe³⁺离子和盐酸环丙沙星药物分子,检测限分别为4.59和0.77 μmol·L^-1。     

具有三重螺旋链的二氯苯氧乙酸铽(Ⅲ)配位聚合物的晶体结构与荧光性质

采用水热法制备了一种新型金属配位聚合物[Tb2(2,4-D)6(2,2'-bipy)2]n(1)(2,4-D=2,4-二氯苯氧乙酸;2,2'-bipy=2,2'-联吡啶),用X-衍射单晶结构分析、红外光谱分析、荧光光谱法对产物进行了结构表征。结构分析表明,标题配合物属于单斜晶系,P2(1)/n空间群,晶胞参数a=2.792(1)nm,b=0.851(3)nm,c=3.335(1)nm,β=113.6470(1)°,V=7.2575(5)nm3,Z=4。金属离子Tb3+处于扭变的四方反棱柱构型中,金属离子之间通过配体2,4-D的羧基的桥联作用,链接成为一维三重螺旋链状配位聚合物。配合物的荧光光谱表明,配合物有望成为潜在的绿光材料。     

四种同构镧系金属有机框架的合成、结构和荧光传感Fe3+和盐酸环丙沙星

采用溶剂热法,以含氮四羧酸3,5-二(3'',5''-二羧苯)-1H-1,2,4-三唑(H₄BDT)为配体,成功合成了4种同构镧系金属有机框架(Ln-MOFs)：{[La₃(BDT)₂(HCOO)(H₂O)₅]·0.5H₂O·3DMF}_n(1)、{[Ce₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n(2)、{[Pr₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n(3)和{[Nd₃(BDT)₂(HCOO)(H₂O)₅]·3DMF}_n(4),并采用单晶X射线衍射、粉末X射线衍射、元素分析、热重、傅里叶换红外光谱、N₂吸附实验和荧光光谱对其进行表征。结果表明,这些Ln-MOFs均为单斜C2/m空间群晶体,是双核为无机建筑单元的三维介孔结构。其中2可选择性荧光检测Fe³⁺离子和盐酸环丙沙星药物分子,检测限分别为4.59和0.77 μmol·L^-1。     

Crystal Structures,Characterizations and Fluorescence Properties of Two 3D Ca(Ⅱ)/Sr(Ⅱ) Coordination Polymers Based on 2-Sulfoterephthalate

Two alkaline earth metal coordination polymers[M(2-Hstp)(H_2O)](M=Ca~(2+)(1)and Sr~(2+)(2),2-H_3stp=2-sulfoterephthalate)were synthesized under hydrothermal conditions by the precursor[Mn(2-Hstp)_2(4,4?-Hbpy)_2]and alkaline earth metal salts.The two alkaline earth complexes are not isomorphic.Complex 1 crystallizes in the monoclinic space group P2_1/m,while2 in the monoclinic space group P2_1/c,despite of their similar formulas.In 1,the Ca~(2+)ion lies in a seven-coordinated pentagon bipyramidal configuration,coordinated with five 2-Hstp~(2-)anions and one water molecule.However,the Sr~(2+)ion in 2 is coordinated by nine oxygen atoms to form a single-capped square antiprism polyhedron.Both 1 and 2 exhibitπ-π*emission of the 2-sulfoterephthalate ligand.     

Investigation of the Crystallization Kinetics of Zn(Met)(AcO)_2·H_2O in Mixed Solution of Water and Acetone by Microcalorimetry

Introduction The complexes of zinc salts with -amino acid as additive have a wide application in medicine, foodstuff and cosmetics.1-3 The synthesis methods of the com-plexes of zinc salts with -amino acid have been re-viewed.4 The solubility of Zn(AcO)2-Met-H2O system at 298.15 K has ever been investigated by the semi-micro-phase equilibrium method.5 The phase diagram is a simple one, in which the solid complex of Zn(AcO)2 and Met can not be obtained at 298.15 K. Zn(Met)2+ in solution w…