四氮［14］轮烯合镍（Ⅱ）配合物的研究（Ⅰ）──取代四氮［14］轮烯合镍（Ⅱ）配合物的合成及其表征

四氮［１４］轮烯类配合物在性质上与卟啉、酞菁类化合物具有许多相似性．本文利用模板反应，合成了２个四氮［１４］轮烯合镍（Ⅱ）配合物及６个四氮［１４］轮烯合镍（Ⅲ）配合物的衍生物，其中６个未见文献报道。对所有化合物进行了ＥＡ、ＩＲ、ＵＶ、１ＨＮＭＲ、ＭＳ等波谱表征．     

四氮杂大环四烯镍(Ⅱ)配合物催化的化学振荡反应

化学振荡反应是化学反应体系中某些状态量随时间或空间周期性变化。四氮杂大环配合物与存在生物体内的一些含有卟吩环的金属酶结构相似。目前,可以催化化学振荡反应的四氮杂大环配合物并不多,文献报道了一种具有Ｃ＝Ｎ共轭双键的四烯型四氮杂大环配体（ＴＩＭ）的Ｎｉ 的配合物可以催化ＢＺ化学振荡反应［１－３］。然而以２,４,４,９．１１,１１一六甲基一１,５,８,１２－四氮杂环十四一１,５, ８, １２一四烯（Ｌ）镍配合物［ＮｉＬ（ＣＩＯ４）２］这种具有四个孤立 Ｃ＝Ｎ双键的四烯型四氮杂大环镍的配合物作为振荡反应催化…     

四氮大环席夫碱配合物研究(Ⅱ)——1,3∶6,7∶10,11∶14,15-四苯并-1,4,9,12-四氮[16]轮烯过渡金属配合物的合成及表征

自从１９６８年Ｊａｇｅｒ合成第一个四氮［１４］大环席夫碱配合物以来［１］，四氮大环席夫碱配合物的研究受到人们很大的关注。这类配体与天然卟啉环非常相似，对小分子如Ｏ２、ＣＯ、ＣＯ２等均有较强的键联能力，对于研究生物体内的金属蛋白质及酶有着重要的意义［２...     

四氮［14］轮烯合镍（Ⅲ）配合物的研究（Ⅱ）──取代四氮［14］轮烯合镍（Ⅱ）配合物的合成及电化学性质

利用模板反应和亲电取代反应，合成了６种互为顺反异构体的四氮［１４］轮烯合镍（Ⅱ）配合物，并用￣１ＨＮＭＲ谱进行了确证．此外，还对一系列四氮［１４］轮烯合镍（Ⅱ）配合物进行了电化学研究．应用瞬态电化学方法和电化学ＥＳＲ波谱对ＣＶ峰进行了讨论与归属；研究了部分大环配合物的成膜现象及成膜机理．     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

铂四元环配合物的重排机理

铂四元环配合物的重排机理张啸（南京大学化学系９４硕２１００９３）美国Ｃｏｒｎｅｌｌ大学化学系的ＲｏａｌｄＨｏｆｆｎ１ａｎｎ获得了１９８１年度的诺贝尔化学奖，在他的获奖演讲中［１］，Ｈｏｆｆｍａｎｎ以铂四元环配合物的重排反应为例，展示了“等叶片模型”在...     

四甲基双硅桥联环戊二烯基稀土金属有要配合物的合成…

四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在ＴＨＦ溶反应合成了标题配合物Ｍｅ４Ｓｉ２（Ｃ５Ｈ４）２ＬｎＣｌ［Ｌｎ：３Ｎｄ，４Ｓｍ，５Ｇｄ，６Ｙ］和配合物Ｍｅ４Ｓｉ２（Ｃ５Ｈ５）２Ｌｎ（Ｃ５Ｈ５）（ＴＨＦ）ｎ［ＬＮ：１Ｌａ，ｎ＝１；２Ｐｒ，ｎ＝０］。通过元素分析、ＨＮＭＲ、＾１３ＣＮＭＲ和ＭＳ确证了配合物的结构，在ＴＨＦ溶液中重结晶获得配合物４的单晶，Ｘ射线衍证明晶体结构为二聚体。４为单斜晶系，空间     

配合物[La(pic)_3(phen)_2]·CH_3CN的合成及晶体结构

随着稀土的广泛应用,稀土多元配合物结构研究逐渐成为一个使人感兴趣的课题［１～６］。对包含双齿杂环胺配体的稀土多元配合物研究开展较早,倪兆艾等对邻菲咯啉—苦味酸阴离子体系萃取稀土元素进行了系统研究［６］;朱龙观等合成镧系邻菲咯啉四元混合阴离子配合物并对晶体结构进行了分析［１,２］;张仲生等对［Ｇｄ（ＮＡ）３（Ｐｈｅｎ）（Ｈ２Ｏ）］·２Ｈ２Ｏ（ＮＡ＝烟酸,Ｐｈｅｎ＝邻菲咯啉的结构进行了研究［３］。本文用苦味酸镧与邻菲咯啉在有机溶剂中反应得到了镧配合物,培养出单晶并对其结构进行研究。１实验１.１配合物的合…     

双亲性邻苯二甲酸正十八醇单酯稀土配合物的合成、发光、能量传递及成膜性能

自从ＶｏｎＨａｎｓＫｕｈｎ［１］首次发表了关于稀土配合物ＬＢ膜的研究以来,随着材料科学的不断发展,功能稀土配合物ＬＢ膜以其在导电［２,３］、非线性光学［４,５］、磁学［６,７］和光学［８,９］等领域中的优异性能愈来愈引起人们的注意,并取得了可喜的进展...     

氯化二氯代四苯基卟啉磷合二氯甲烷的晶体结构

氯化二氯代四苯基叶啉磷（Dichloro（5，10，15，20－tetraphenylporphinato）－phosphorus（V）chloride，［PCl2TPP］Cl）是典型的非金属卟琳配合物．据文献报导［1］该配合物能够与噻吩类化合物反应，所得单体经电解氧化，可生成具有导电性的聚合物．因此，测定［PCl2TPP］Cl的分子结构有着十分重要的意义．1标题化合物的制备及单晶生长标题化合物技文献［2］合成．用于X－射线衍射的单晶样品是将标题化合物的二氯甲烷／正庚烷混合溶液静置数周后得到的．单晶为紫色，用于X－射线衍射测定的晶粒尺寸为0．38mm×0．38mm×0．28mm．…     

5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌配合物的合成表征

设计合成了5种未见文献报道的5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌金属配合物,并用IR,UV-Vis,1H NMR,元素分析以及XPS对其组成和结构进行了表征,研究了这10种酰胺基系列卟啉化合物的拉曼光谱和荧光光谱的变化.结果显示链长对荧光和拉曼光谱没有明显影响,其取代基效应基本相同,配体的荧光强度强于锌配合物的荧光强度.在拉曼光谱中,由于卟啉分子平面的对称性由D2h变为D4h群及其锌离子d轨道的电子效应,卟啉配体和锌配合物之间的拉曼光谱有很大差别.     

Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.     

DNA-binding properties studies and spectra of a novel fluorescent Zn(II) complex with a new chromone derivative

A new chromone derivative (6-ethoxy chromone-3-carbaldehyde benzoyl hydrazone) ligand (L) and its two transition metal complexes [Zn(II) complex and Ni(II) complex] have been prepared and characterized on the basis of elemental analysis, molar conductivity, mass spectra, UV–vis spectra and IR spectra. The Zn(II) complex exhibits light blue fluorescence under UV light, and the fluorescent properties of Zn(II) complex and the ligand in solid state and in different solutions (MeOH, DMF, THF and H₂O) were investigated. In addition, the interactions of the Zn(II) complex and the ligand with calf thymus DNA were investigated using UV–vis absorption, fluorescence, circular dichroic spectral methods and viscosity measurement. It was founded that both two compounds, especially the Zn(II) complex, strongly bind with calf thymus DNA, presumably via an intercalation mechanism.     

水杨醛-4-甲氧基苯甲酰腙识别锌离子的研究

设计合成了荧光传感分子水杨醛-4-甲氧基苯甲酰腙(SAMB),通过IR、1HNMR和元素分析确证了其结构,利用紫外-可见吸收光谱和荧光光谱考察了其对不同阳离子的识别作用。结果表明,SAMB的荧光发射对锌离子表现出高选择性响应,且形成1∶1型配合物。乙醇中锌离子的加入导致SAMB的荧光增强328倍,而其他过渡金属离子只引起SAMB的荧光的略微增强。初步探讨了受体分子与锌离子的结合模式与荧光增强机理。     

FLUORESCENCE LINE NARROWING SPECTROSCOPY OF Zn PORPHYRINS*

Fluorescence line narrowing (FLN) spectroscopy was used to study the vibrational features of Zn porphyrins, including Zn octaethylporphine, Zn mesoporphyrin, Zn deuteroporphyrin and Zn coproporphyrin, and the interaction of these porphyrins with their solvent matrices. A number of ground-state vibrational levels were identified for each of the Zn porphyrins. Six of these levels persistent throughout almost all spectra were analyzed in terms ofcontributions of specific internal vibrational modes of the porphyrins. A number of other vibrational levels were identified as characteristic of the peripheral substituents of Zn porphyrin. Phonon wing contribution in the FLN spectra increased with increased polarity of the solvent matrix, and the Stokes shift calculated from the conventional spectra was correlated with the strength of phonon coupling. Specific vibrational modes were found to couple differently with the solvent and to have different phonon wings. The conventional and energy-selected spectra of Zn coproporphyrin in 5 M guanidine HCI suggest that guanidine ligates to the Zn atom.     

2,2''''—双〔2—(邻甲酰肟苯氧基)乙基〕醚与过渡金属配合物的合成及性质研究

含氮配位原子的希夫碱型化合物在分析化学、合成化学、药学等方面有广泛的应用。近十多年来,随着新药物的研制和生物无机化学的发展,其研究正在不断深入。肟类化合物在结构上与希夫碱型化合物主要不同之处是在于它与氮原子相连的基团是羟基,它在适当的条件下可参与金属配位或形成氢键,研究其配位模式有较重要的理论意义。我们合成了一个新的含醚氧链的双肟化合物,2,2＇—双[2—(邻甲酰肟苯氧基)乙基]醚(H_2BFO)。本     

Enhanced Photoelectrochemical Property of Zn Loaded TiO2 Nanotube Arrays Electrode

TiO₂ nanotube arrays (TNTs) electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled bychronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.     

具有分子内折叠结构锌配合物的合成，与DNA键合及其对DNA切割作用研究

本文报道了一个锌配合物[Zn(bipy)(pmal)(H2O)]·2H2O（其中bipy = 2,2’-联吡啶, pmal = 苯基丙二酸）的合成,晶体结构及其光谱学研究。并通过单晶X射线衍射,元素分析,红外光谱等手段对它进行了表征。同时,利用紫外光谱和荧光光谱方法考察了该配合物与小牛胸腺DNA的键和作用。琼脂糖凝胶电泳实验的结果说明该配合物的平面结构对pBR 322DNA切割作用显著。     

卡尔曼滤波法解析严重重叠的荧光峰

锌、铝同７－碘－８羟基喹啉－５－磺酸－溴化十六烷基三甲铵形成的络合物荧光光谱严重重叠，分离度仅为０．２６。本文以该体系为例，着重考察了卡尔曼滤波法解析谱峰严重重叠体系的潜力。结果表明，在锌、铝络合物峰值处，当铝络合物的荧光强度小于锌络合物的荧光强度时，二者均可得到满意的分析结果，当铝络合物的荧光强度大于锌络合物的荧光强度时，锌的分析结果显著变差。在此情况下，用卡尔曼滤波法处理同步荧光光谱数据，分析     

3-甲基吡唑-5-甲酸基Zn(Ⅱ)配合物的合成、晶体结构及荧光性质

A transition metal complex Zn(mpc)₂(H₂O)₂ (Hmpc=3-methylpyrazole-5-carboxylic acid) has been synth-esized by the reaction of Hmpc with Zn(NO₃)₂·6H₂O using hydrothermal method, which was characterized by IR spe-ctra, elemental analysis and single-crystal X-ray structure analysis. The structure reveals that the complex crystallizes in the trigonal space group R3c with the Zn^Ⅱ atom on a threefold axis, composed of one Zn^Ⅱ atom, two independent mpc^- ligands and two coordinated water. Hydrogen bonds link the molecules into a three-dimensional supramolecular architecture. Fluorescent analysis in the dilute EtOH solution shows that the title complex exhibits a broad fluorescent band at 471 nm upon photoexcitation at 280 nm and has a bathochromic shift of the emission energy compared with the free ligand, possibly due to metal-to-ligand charge transfer (MLCT). CCDC: 682402.