新型双核锌席夫碱配合物的合成及其结构表征

新型双核锌席夫碱配合物的合成及其结构表征;席夫碱; 双核锌配合物; 合成; 谱学表征; 构象分析     

不对称席夫碱过渡金属配合物的合成和催化性能

用乙二胺、乙酰丙酮与水杨醛反应合成了一种不对称四齿席夫碱配体(H2L)及其铜、钴、镍、锌配合物,通过元素分析、摩尔电导、红外光谱、紫外光谱、X-射线光电子能谱等手段对配体及其配合物进行了表征,并推测所有配合物均为烯醇式四配位结构,确定新配合物的组成为MC14H16N2O2(M=Cu,Co,N i,Zn)。并研究了配合物对双氧水的催化分解性能。     

乙二胺-2-吡啶甲醛席夫碱钯配合物的制备、表征及其催化性能研究

利用2-吡啶甲醛和乙二胺制得乙二胺-2-吡啶甲醛席夫碱配体,再与钯盐作用制得乙二胺-2-吡啶甲醛席夫碱钯配合物.运用红外光谱、核磁共振、质谱、元素分析、ICP等分析手段对乙二胺-2-吡啶甲醛席夫碱配体及其钯配合物进行了表征,提出了乙二胺-2-吡啶甲醛席夫碱钯配合物的结构,并对其在Heck反应中的催化性能进行了研究.     

乙二胺-2-吡啶甲醛席夫碱钯配合物的制备、表征及其催化性能研究

摘要：本文利用2-吡啶甲醛和乙二胺制得乙二胺-2-吡啶甲醛席夫碱配体,再与钯盐作用制得乙二胺-2-吡啶甲醛席夫碱钯配合物。运用红外光谱、核磁共振、质谱、元素分析、ICP等分析手段对乙二胺-2-吡啶甲醛席夫碱配体及其钯配合物进行了表征,提出了乙二胺-2-吡啶甲醛席夫碱钯配合物的结构,并对其在Heck反应中的催化性能进行了研究。     

吸电子基团对席夫碱及其钯配合物在抑菌及催化活性方面的影响

报道了2,6-二异丙基苯胺缩苯甲醛或2,4-二氯苯甲醛席夫碱(L1和L2)及其钯配合物(1和2)的合成,并通过元素分析、红外光谱、X-射线单晶衍射等方法对席夫碱配体及配合物进行了表征。通过与已报道的席夫碱L1及其钯配合物1结构相比较,发现引入吸电子取代基合成的一个新的席夫碱及其钯配合物(L2和2)对抑菌及催化活性有较大影响。抑菌活性试验表明,配体及配合物均具有良好的抑菌活性,配合物相对于配体具有更好的抑菌效果,配体苯环上的吸电子取代基能有效提高抑菌活性。研究了两组配合物(1和2)对溴代苯和丙烯酸Heck交叉偶联生成苯丙烯酸的催化性能,考察了不同反应因素(缚酸剂种类、反应温度及溶剂)对该反应的影响,确定了反应的最佳条件;催化实验结果显示吸电子基团的引入增加了钯配合物的空间位阻效应进而降低其催化活性。     

吸电子基团对席夫碱及其钯配合在抑菌及催化活性方面的影响

报道了2, 6-二异丙基苯胺缩苯甲醛或2, 4-二氯苯甲醛席夫碱(L1和L2)及其钯配合物(1和2)的合成, 并通过元素分析、红外光谱、X-射线单晶衍射等方法对席夫碱配体及配合物进行了表征。通过与已报道的席夫碱L1及其钯配合物1结构相比较, 发现引入吸电子取代基合成的一个新的席夫碱及其钯配合(L2和2)对抑菌及催化活性有较大影响。抑菌活性试验表明, 配体及配合物均具有良好的抑菌活性, 配合物相对于配体具有更好的抑菌效果, 配体苯环上的吸电子取代基能有效提高抑菌活性。研究了两组配合物(1和2)对溴代苯和丙烯酸Heck交叉偶联生成苯丙烯酸的催化性能, 考察了不同反应因素(缚酸剂种类、反应温度及溶剂)对该反应的影响, 确定了反应的最佳条件;催化实验结果显示吸电子基团的引入增加了钯配合物的空间位阻效应进而降低其催化活性。     

水杨醛天冬氨酸过渡金属配合物的ESR波谱及抗O_2~(·-)性能

测定了水杨醛天冬氨酸Cu（Ⅱ）配合物在室温和低温下吡啶中的溶液ESR谱,室温溶液谱观测到二级效应和弛豫效应,给予了理论解释,计算了弛豫参数;根据低温ESR波谱参数,计算了键参数,讨论了配合物的成键特性和稳定性。利用ESR法直接测定了水杨醛天冬氨酸席夫碱配体及其钢、锌、钻、镍配合物抗O2-性能,结果表明：配体和配合物均有抗O2-性能,配合物清除能力比配体强,其中铜配合物清除O2-能力最强。     

甲硫氨酸席夫碱铜、锌、钴配合物合成及抗O_2~·-性能

合成了邻香草醛甲硫氨酸席夫碱及其铜、锌、钴等配合物 ,通过元素分析、摩尔电导、红外光谱、电子光谱、热分析及电子顺磁共振等手段对它们进行了表征 ,并用 EPR法探讨了它们对O· -2 的清除作用 .结果表明 ,配体与配合物均具有抗 O· -2 性能 ,配合物清除能力比配体强 ,其中铜和钴配合物清除能力最强     

甲硫氨酸席夫碱铜、锌、钴配合物合成及抗O·-2性能

合成了邻香草醛甲硫氨酸席夫碱及其铜、锌、钴等配合物,通过元素分析,摩尔电导、红外光谱、电子光谱、热分析及电子顺磁共振等手段对它们进行了表征,并并用ＥＰＲ法探讨了它们对Ｏ＾．－２的清除作用,结果表明,配体与配合物均具有抗Ｏ＾．－２性能,配合物清除能力比配体强,其中铜和钴配合物清除能力最强。     

手性席夫碱配合物用于催化不对称环氧化

手性席夫碱过渡金属配合物可以高效催化烯烃不对称环氧化反应,因此其合成及催化性能研究一直以来受到广泛的关注.本文较详细地综述了最近十年来合成的手性席夫碱过渡金属配合物及其对烯烃环氧化反应的催化性能的研究进展.重点讨论了新型的对称和非对称salen型配体过渡金属配合物的合成及其应用,分析探讨了手性席夫碱过渡金属配合物作为催化剂的优缺点、催化机理和未来发展方向.     

Syntheses and structures of 2-bromo-4-chloro-6- (cyclopropyliminomethyl)phenol and its zinc(II) complex

A new Schiff-base ligand 2-bromo-4-chloro-6-(cyclopropyliminomethyl)phenol and its zinc(II) complex have been synthesized and characterized by elemental analyses, infrared spectroscopy, ¹H NMR, ¹³C NMR, and single crystal X-ray determinations. The ligand and the complex crystallized in the space groups Pnma and P2₁/c, respectively. In the complex, the Zn atom is four-coordinate tetrahedral coordination with two imine N and two phenolate O atoms from two Schiff-base ligands. The bond lengths related to the donor atoms in the complex are different from those in the ligand. The coordination of the ligand to the zinc also was supported by IR spectra.     

Synthesis,crystal structure,and biological activities of a Zn(II) complex with a Se substituted Schiff base

A Zn(II) complex with an organoselenium substituted Schiff base, bis{2-[(benzylimino)methyl]-4,6-dihydroselenophenol}Zn(II), has been synthesized and characterized by elemental analyses and X-ray diffraction. Zn(II) is four-coordinated by two phenolate O and two imine N from two organoselenium substituted Schiff-base ligands, forming a distorted tetrahedral geometry. The title complex and its ligand were tested in vitro for their antibacterial and antitumor activity with the complex showing higher antibacterial and antitumor activities.     

功能化多壁碳纳米管填充的凝胶电解质在染料敏化太阳能电池的应用

纯聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)基凝胶电解质常常受制于低离子电导率,阻碍了其在染料敏化太阳电池(dye-sensitized solar cells,DSSCs)中的应用。 而利用纳米填充可提高凝胶电解质离子电导率及凝胶电解质DSSCs的性能。 本文使用功能化的多壁碳纳米管(f-MWCNT)作为PVDF-HFP凝胶电解质的纳米填充物,通过改变f-MWCNT的质量分数来研究其对电解质的离子电导率和离子扩散的影响,进而研究其对DSSCs的转化效率和长期稳定性的增强作用。 研究发现:质量分数0.5%的f-MWCNT明显提高了PVDF-HFP凝胶电解质的离子电导率和离子扩散系数。 并且,该凝胶电解质基DSSCs的光转换效率可达5.28%,相比于未填充的PVDF-HFP凝胶电解质基DSSCs(4.01%),其效率提高了31.7%。 42 d后,该电池依然可以保持最初转化效率的86.5%。 实验结果证实了f-MWCNT在纳米填充方面的巨大潜能,为采用纳米填充物提高凝胶电解质DSSCs的性能提供参考。     

Synthesis,Characterization and Electronic Properties of a Symmetric Bidentate Schiff-Base Ligand and Its Complex with CadmIum(II)

A symmetric bidentate Schiff-base ligand and its complex with Cd(II) is described. The ligand and its complex were characterized by microanalysis, UV-Vis, GC-Mass and FT-IR spectroscopic methods. The present work also studied the structures and electronic properties of the bidentate Schiff-base ligand by using ab initio and AM1 molecular orbital methods. Ab initio and AM1 geometrical predictions have been compared. The analysis of molecular orbitals (MOs) indicates that the N(3) and N(6) atoms could be the coordination sites in this ligand.     

Design and synthesis of a near infra-red luminescent hexanuclear Zn-Nd prism

The use of the Schiff-base ligand N,N'-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine (H2L) and 1,4-benzenedicarboxylate (BDC) enables the construction of the hexanuclear luminescent Zn-Nd complex [Zn4Nd2L4(1,4-BDC)2].[Nd(NO3)5(H2O)].Et2O.2EtOH.3H2O.     

Prevention and mechanism effect of Zn(II) coordination complex on oral implant restoration

In this study, by reaction of Zn(NO₃)₂·6H₂O with HL ligand under a slow evaporation reaction condition, a novel mononuclear Zn(II) complex [Zn(L)₂]·C₂H₅OH (1) with tetrahedral coordination geometry has been created by employment of an adamantan-type Schiff-base ligand 2-(adamantan-1-ylimino)methyl-4-methylphenol (HL). Its application values against the recurrent infection after oral implants were evaluated with ELISA assay and real time RT-PCR assay. The Zn(II) complex toxicity was evaluated in this research with CCK-8 assay. The molecular docking simulation confirmed that the adamantane functional group applied a hindrance effect on the connected nitrogen atom and therefore, the oxygen atom on the hydroxyl functional group could form binding interaction with receptor as expected.     

Organic dye bearing asymmetric double donor-π-acceptor chains for dye-sensitized solar cells

A novel efficient metal free sensitizer containing asymmetric double donor-π-acceptor chains (DC) was synthesized for dye-sensitized solar cells (DSSCs). Comparing to 3.80%, 4.40% and 4.64% for the DSSCs based on the dyes with single chain (SC1, SC2) and cosensitizers (SC1 + SC2), the overall conversion efficiency reaches 6.06% for DC-sensitized solar cells as a result of its longer electron lifetime and higher incident monochromatic photon-to-current conversion efficiency.     

SYNTHESIS,CRYSTAL STRUCTURE AND NONLINEAR OPTICAL PROPERTIES OF THIOSEMICARBAZONE ZINC COMPLEX

Abstract

A new zinc bromide complex of a Schiff-base ligand derived from thiosemicarbazide and 4-methoxylphenyldehyde, which shows ca 13 times better SHG efficiency than urea, has been prepared and characterized. Single crystal X-ray diffraction analysis established that the coordination geometry about the zinc atom is tetrahedral with two equivalent Zn-Br and Zn-S bonds. The Schiff-base ligand is coordinated to the Zn(II) via the monodentate mercapto sulfur atom. The polar structure (space group Aba2) is stabilized by hydrogen bonds between the oxygen atom and the amino nitrogen atoms N(l).

The complex crystallizes in the orthorhombic space group Aba2 with cell parameters a=11.970(2), b = 21.888(2), c= 9.157(2)Å and Z = 4. The structure was solved by direct methods and refined by full-matrix least-squares to R = 0.065 and R _w = 0.117 for the 722 observed reflections with I > 2[sgrave](I).     

Infrared and DNA-binding on ultraviolet and fluorescence spectra of new copper and zinc complexes with a naringenin Schiff-base ligand

A naringenin Schiff-base ligand (H(3)L) and its copper(II) and zinc(II) complexes have been synthesized and characterized by elemental analyses, molar conductivities, (1)H NMR, IR spectra, UV spectra and thermal analyses. The DNA-binding properties of the Cu(II) and Zn(II) complexes have been investigated by fluorescence spectroscopy, ultraviolet spectroscopy and by viscosity measurements. The results indicate that complexes and ligand may bind to DNA by intercalation modes, but the binding affinity of the complexes is much higher than that of the ligand.     

有机染料D-SS和D-ST用于染料敏化太阳能电池光敏剂的比较

为了揭示D-SS和D-ST分子敏化的染料敏化太阳能电池(DSSCs)的物理机制,采用密度泛函理论(DFT)、含时密度泛函理论(TDDFT)和自然键轨道(NBO)分析,模拟计算染料D-SS和D-ST分子的结构、紫外-可见吸收光谱和能级结构.D-SS的紫外-可见吸收光谱相比于D-ST的有明显的红移,而且D-SS分子的摩尔吸光系数也高于D-ST分子的.D-SS分子本应该比D-ST分子拥有更高的俘获太阳辐射光子的能力,但由于D-SS分子的最高占据分子轨道(HOMO)能级位置比氧化还原电解质(|-/|-3)的氧化还原能级高,处于光激发态的D-SS分子向TiO2电极注入电子而被氧化后,不能顺利地从电解质中得到电子而还原,使得D-SS分子俘获光子的能力不能充分发挥,从而严重地降低了由其敏化的DSSCs的光电性能和光电能量转换效率.揭示了D-SS敏化的DSSCs的光电性能,特别是光电能量转换效率比D-ST敏化的DSSCs的低的原因.染料敏化剂分子的HOMO能级的位置对于DSSCs来说也是很重要的,用于DSSCs的有机敏化剂分子的HOMO能级的位置必须低于氧化还原电解质的氧化还原能级.