以三(4-咪唑基苯基)胺为配体的镉配合物的合成、晶体结构和荧光性质

以三(4-咪唑基苯基)胺(TIPA)和碘化镉为原料,分别与环已二酸(H_2CDC)和5-甲基间苯二甲酸(H_2MPDA)在水热条件下反应,得到2个结构不同的配位聚合物[CdI(TIPA)(CDC)_(0.5)]_n(1)和{[Cd(TIPA)(MPDA)]·H_2O}_n(2)。对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。单晶结构分析显示,配合物1拥有二维两重贯穿的(3,4)-连接的(4.5~2)(4.5~3.7~2)拓扑结构,层与层之间通过弱相互作用连接成三维超分子结构;而配合物2具有二维(3,5)-连接的(4~2.6~7.8)(4~2.6)拓扑的层状结构,层与层之间通过互锁方式连接成三维金属有机骨架。结果说明了有机羧酸在配合物组装过程中起着非常重要的作用。此外,在室温下对2个配合物进行了荧光性质分析。     

分子基磁体[NCBzPy][Ni(dmit)2]的合成、表征和磁学性质

合成了一种新的取代苄基吡啶盐[NcBzpy]cl(1),1和NiCl2,dmit^2-反应生成分子基磁体[NCBzPy][Ni(dmit)2](2),其结构用元素分析、IR和UV进行了表征。并测定了2在2K～300K的变温磁化率,结果显示。相邻Ni^3 之间存在铁磁偶合作用。     

以4,4'-联苯二甲酸和咪唑基化合物为配体的钴配合物的合成和晶体结构

以4,4′-联苯二甲酸（H₂BPDC）和4,4′-二咪唑基二苯醚（BIDPE）为原料,与硝酸钴在不同温度下反应,得到2个结构不同的配位聚合物{[Co₂（BPDC）₂（BIDPE）₂（H₂O）]·2H₂O}_n（1）和{[Co（BPDC）（BIDPE）]·H₂O}_n（2）。对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。配合物1属于单斜晶系,C2/c空间群,a=1.456 02（15）nm,b=1.557 51（16）nm,c=2.522 6（3）nm,β=90.834 0（10）°,V=5.720 2（10）nm3,Z=4,Mr=1 256.98,Dc=1.460 g·cm-3,μ=0.655,F（000）=2 592,R1=0.036 7,w R2=0.087 5（I>2σ（I））。配合物2属于三斜晶系,P1空间群,a=1.061 92（10）nm,b=1.098 51（11）nm,c=1.324 51（13）nm,α=112.725 0（10）nm,β=92.112 0（10）°,γ=96.574 0（10）°,V=1.410 2（2）nm3,Z=2,Mr=619.48,Dc=1.459 g·cm-3,μ=0.662,F（000）=638,R1=0.047 4,w R2=0.116 5（I>2σ（I））。单晶结构分析显示,配合物1拥有一维链状结构,而配合物2具有二维两重贯穿结构,并表现出聚轮烷的结构特征。结果说明了反应温度在配合物组装过程中起着非常重要的作用。     

氨基酸类高分子药物合成方法的研究

用无机强酸催化酯化反应，合成了聚乙烯醇(PVA)与甘氨酸、丙氨酸的聚合物。对反应条件进行了考察，获得了具有高转化率、高纯度的最佳工艺条件。结果表明：以DMSO为溶剂，PVA浓度在3％以下，pH为3—5，温度控制在120℃一130℃，反应10h一16h后，甘氨酸转化率达44．1％，丙氨酸转化率达33．9％。     

以环已二酸及咪唑基化合物为配体的镉配合物的合成、晶体结构及荧光性质

以硝酸镉、环已二酸(H₂CDC)和2,3,5,6-四氟-1,4-二咪唑基二甲苯(FBIX)为原料,在水热条件下得到了1个配位聚合物[Cd(CDC)(FBIX)_0.5]_n(1),并利用元素分析、红外光谱以及X-射线单晶洐射对其进行了表征。该晶体属三斜晶系,P1 空间群,a=0.880 53(18) nm,b=0.888 31(18) nm,c=1.091 7(2) nm,α=97.349(2)°,β=95.688(2)°,γ=105.495(2)°,V=0.808 1(3) nm³,D_c=1.799 g·cm^-3,Z=2,F(000)=434,Goof=1.094,R₁=0.025 6,wR₂=0.072 3。Cd(Ⅱ)离子通过2个CDC配体桥联形成一维双绞链,再通过FBIX配体连接成二维层状结构。室温下该配合物表现出较强的荧光发射。     

新型吡啶双羧酸席夫碱配体锌配合物的合成、晶体结构及荧光性质(英文)

A novel pyridyl-dicarboxylate Schiff-base ligand (5-((pyridin-3-ylmethyl)amino)isophthalic acid,H2L) and its Zinc(Ⅱ) complex,namely,ZnL (1),were synthesized. The ligand was characterized by NMR analysis. The X-ray crystallographic analysis on complex 1 shows that 1 crystallizes in homoclinic,space group P21/c with a= 0.753 83(10) nm,b=1.040 52(14) nm,c=1.734 67(19) nm,β=112.123(5)°,V=1.260 5(3) nm3,Z=4,Dc=1.769 g· cm-3,F(000)=680,μ=1.966 mm-1,the final R=0.030 8,wR=0.085 6. In complex 1,the coordination environment of Zn(Ⅱ) is distorted tetragonal-pyramid with N1O4 set. The 2D 4,4-topological sheets in 1 packed along a axis to form its 3D framework,which was stabilized by the π…π interactions between the adjacent aromatic rings on the neighbouring sheets. The photoluminescent property of 1 was also investigated.     

二维配合物{[Cd(bpds)(bpp)_2]·2H_2O}_n的水热合成、晶体结构和荧光性质研究(英文)

A novel two-dimensional cadmium(Ⅱ) complex {[Cd(bpds)(bpp)2]·2H2O}n (1) with 4,4′-biphenyldisulfonic acid (H2bpds) and 1,3-bis(4-pyridyl)propane (bpp) has been synthesized by means of hydrothermal method and characterized by elemental analysis, IR spectrum, thermal analysis and single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a=0.900 96(12) nm, b=1.098 84(14) nm, c=1.125 71(15) nm, α=115.907(2)°, β= 92.307 (2)°, γ=105.383 (2)°, V=0.950 8(2) nm3, Dc=1.497 g·cm-3, Z=1, F(000)=440, Goof=1.046, R1=0.028 2, wR2= 0.074 9. Complex 1 shows a novel two-dimensional (2D) lamellar structure and further extended into a 3D supramolecular structure through O-H…O and C-H…O hydrogen bonding interactions. Luminescent studies show that complex 1 exhibits intense blue fluorescent emission. CCDC: 769593.     

二维配合物[Cd_3(HBTA)_2(BIPA)_3]_n的水热合成、晶体结构和荧光性质研究(英文)

<正>Great interest has been focused on the rapidly expanding field of the construction of novel functional metal-organic frameworks(MOFs)owing to their variety of intriguing architectures and topologies and their potential applications in magnetism     

Synthesis,Crystal Structure,and Magnetic Properties of a Quasi-one-dimensional Compound Based on TCNQ

A novel compound, （IBzQI）（TCNQ）2 2 （IBzQ1=1-（4-iodobenzyl）quinolinium and TCNQ = 7,7,8,8-tetracyanoquinodimethane） has been fabricated and X-ray single-crystal structurally analyzed. This compound crystallizes in the triclinic system, space group P1 with a = 8.3540（17）, b = 13.284（3）, c = 16.185（3） А, α= 82.12（3）, β= 75.19（3）, γ= 72.34°, V = 1651.2（6） А^3, Z= 2, C_40H_21IN_9, Mr = 754.56, Dc = 1.518 g/cm^3,μ= 1.015 mm^-1, S = 1.010, F（000） = 754, R = 0.0387 and wR = 0.0948. The structure analysis shows that the anions are stacked into column with tetrads, and there are two types of TCNQ entries （TCNQ-1 and TCNQ^0） in agreement with the IR spectra analysis of the compound. The temperature dependence of the magnetic susceptibility （2-300 K） for 2 exhibits spin gap of singlet-triplet feature, and the best fit gave △/kB = 1523.4 K. In order to understand both magnetic behavior and local charge distribution of [（TCNQ）2]-unit, the molecular orbital calculations and analysis based on extended Hückel method were performed, and the results support the analyses of both crystal structure and IR spectra.     

2-取代芳基菲并咪唑类化合物的电子结构和光谱性质的理论研究

运用密度泛函理论,在B3LYP/6-31G(d)水平上对菲并咪唑(PI)及其8种2-取代芳基衍生物的结构进行了全优化,探讨了取代基对分子结构、电离势(I_P)、电子亲和势(E_A)、电荷转移、前线分子轨道能量和电子吸收光谱等方面的影响.采用含时的度泛函理论(TD-DFT)计算了各分子的气相及液相的电子吸收光谱,计算结果与实验值十分接近.并用GaussSum2.1程序模拟吸收光谱和态密度(DOS)图,结果表明,芳基4′-位上取代基对菲并咪唑(PI)和苯环的骨架结构没有很大的扰动,但它们重新调整了菲并咪唑环和苯环中原子电荷分布,前线分子轨道(LUMO)-HOMO)能隙降低,导致8种取代的化合物的吸收波长均发生了红移.