共查询到19条相似文献,搜索用时 109 毫秒
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合成了反丁烯二酰基桥连的3种带不同取代基的卟啉二联体, 通过红外光谱, 紫外-可见光谱, 核磁共振波谱和质谱对化合物的结构进行了确认, 并研究了二联体的表面光电压谱, 荧光光谱和激光拉曼光谱的变化. 结果表明, 取代基的类型对卟啉二联体分子的荧光量子产率有显著影响, 带供电子基团的甲氧基增强了荧光量子产率, 而带吸电子基团的氯则降低了荧光量子产率, 并且吸电子基团的氯比供电子基团的甲氧基对荧光的影响更大. 取代基的电子效应对卟啉二联体的荧光性和激光拉曼光谱有较大影响. 相似文献
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卟啉类化合物不仅在自然界中广泛存在,而且在分子自组装、生物仿生、电化学、分析化学、催化化学等诸多领域都具有广泛的应用。卟啉因中位取代基的种类、数量和性质不同,所表现出来的化学性质也不相同,因此引起了有机工作者的广泛关注。本文首先简单地介绍了卟啉类化合物的基本结构特点和物理、化学性质;然后以结构相对简单的四苯基卟啉为对象,讨论了其合成反应机理;接着重点阐述了不对称中位取代卟啉的3种合成方法,即混合缩合法、全合成法和功能化预先形成法;最后对近年来国内外关于卟啉类化合物的研究状况进行了总结,并对其广阔的发展和应用前景进行展望。 相似文献
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70年代以来,金属卟啉无机小分子配合物日益受到重视。NO可以与金属卟啉形成配合物,并且自身被活化。目前关于原卟啉Ⅸ二甲酯铁、四苯基卟啉铁和八乙基卟啉铁的NO配合物研究已有一些报道,但有取代基的四苯基卟啉体系研究甚少。为深入考察不同取代基活化NO的规律,我们合成了五配位的四(对-硝基苯基)卟啉铁-氧化氮配合物[简称[T(p-NO_2)PP]Fe(Ⅱ)(NO)],并研究了它的光谱性质。 相似文献
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通过密度泛函理论计算比较性地研究了5,15-二(4-(5-乙酰基硫戊氧基)苯基)自由卟啉及其锌配合物的分子结构、电荷性质、分子轨道、电子吸收光谱和红外光谱.这类化合物具有在卟啉相对的两个中位的苯环上连有5-乙酰基硫戊氧基的新颖结构.模拟得到的这两个化合物的分子结构和电子吸收光谱以及红外光谱都与实验测得的符合得很好.通过与未取代的自由卟啉和卟啉锌的结构和性质进行比较,研究了中位取代基、极性溶剂和中心金属取代对此类卟啉化合物结构和性质的影响规律.对化合物的电子吸收光谱中的电子跃迁本质进行了归属,并通过基于正则坐标分析产生的动画对红外光谱的振动模式进行了指认.目前的工作将对理解此类新颖卟啉化合物的结构和性质以及取代基和溶剂效应提供很大的帮助. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(39):11896-11901
Zinc‐induced oligomerization of amyloid‐β peptide (Aβ) produces potentially pathogenic agents of Alzheimer's disease. Mutations and modifications in the metal binding domain 1–16 of Aβ peptide crucially affect its zinc‐induced oligomerization by changing intermolecular zinc mediated interface. The 3D structure of this interface appearing in a range of Aβ species is a prospective drug target for disease modifying therapy. Using NMR spectroscopy, EXAFS spectroscopy, mass spectrometry, and isothermal titration calorimetry the interaction of zinc ions with Aβ fragments 1–7 and 1–10 carrying familial Taiwanese mutation D7H was studied. Zinc ions induce formation of a stable homodimer formed by the two peptide chains fastened by two zinc ions and stacking interactions of imidazole rings. A binuclear zinc interaction fold in the dimer structure was discovered. It can be used for designing zinc‐regulated proteins and zinc‐mediated self‐assembling peptides. 相似文献
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Fluorescent Cross‐Linked Supramolecular Polymer Constructed by Orthogonal Self‐Assembly of Metal–Ligand Coordination and Host–Guest Interaction
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Xiaomin Qian Dr. Weitao Gong Dr. Xiaopeng Li Le Fang Xiaojun Kuang Prof. Guiling Ning 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(20):6881-6890
A new host molecule consists of four terpyridine groups as the binding sites with zinc(II) ion and a copillar[5]arene incorporated in the center as a spacer to interact with guest molecule was designed and synthesized. Due to the 120 ° angle of the rigid aromatic segment, a cross‐linked dimeric hexagonal supramolecular polymer was therefore generated as the result of the orthogonal self‐assembly of metal–ligand coordination and host–guest interaction. UV/Vis spectroscopy, 1H NMR spectroscopy, viscosity and dynamic light‐scattering techniques were employed to characterize and understand the cross‐linking process with the introduction of zinc(II) ion and guest molecule. More importantly, well‐defined morphology of the self‐assembled supramolecular structure can be tuned by altering the adding sequence of the two components, that is, the zinc(II) ion and the guest molecule. In addition, introduction of a competitive ligand suggested the dynamic nature of the supramolecular structure. 相似文献
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Cyril Martini Dr. Guillaume Poize Daniel Ferry Dr. Daiki Kanehira Noriyuki Yoshimoto Dr. Jörg Ackermann Dr. Frédéric Fages Prof. Dr. 《Chemphyschem》2009,10(14):2465-2470
We describe herein the design, synthesis and detailed structural characterization of hybrid 1D nanostructures. They are prepared by supramolecular self‐assembly of oligothiophene molecules on the surface of zinc oxide nanorods in solution at room temperature. Electronic absorption spectroscopy and X‐ray diffraction show that both organic and inorganic components in the coaxial p–n heterojunctions are crystalline. Especially, it is demonstrated that the organic compounds form a self‐assembled monolayer at the surface of the nanorods, which is not the case when zinc oxide quantum dots are instead used. As a result of their hybrid nature, the 1D nanostructures lead to ambipolar semiconducting nanostructured materials as active layers in field‐effect transistors. 相似文献
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Bending Nanofibers into Nanospirals: Coordination Chemistry as a Tool for Shaping Hydrophobic Assemblies
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Dr. Elizaveta Kossoy Dr. Haim Weissman Prof. Dr. Boris Rybtchinski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):166-176
In the current work, we demonstrate how coordination chemistry can be employed to direct self‐assembly based on strong hydrophobic interactions. To investigate the influence of coordination sphere geometry on aqueous self‐assembly, we synthesized complexes of the amphiphilic perylene diimide terpyridine ligand with the first‐row transition‐metal centers (zinc, cobalt, and nickel). In aqueous medium, aggregation of these complexes is induced by hydrophobic interactions between the ligands. However, the final shapes of the resulting assemblies depend on the preferred geometry of the coordination spheres typical for the particular metal center. The self‐assembly process was characterized by UV/Vis spectroscopy, zeta potential measurements, and cryogenic transmission electron microscopy (cryo‐TEM). Coordination of zinc(II) and cobalt(II) leads to the formation of unique nanospiral assemblies, whereas complexation of nickel(II) leads to the formation of straight nanofibers. Notably, coordination bonds are utilized not as connectors between elementary building blocks, but as directing interactions, enabling control over supramolecular geometry. 相似文献
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Francesca Matino Dr. Valentina Arima Dr. Manuel Piacenza Dr. Fabio Della Sala Dr. Giuseppe Maruccio Dr. Ray J. Phaneuf Prof. Roberta Del Sole Dr. Giuseppe Mele Dr. Giuseppe Vasapollo Prof. Giuseppe Gigli Prof. Roberto Cingolani Prof. Ross Rinaldi Prof. 《Chemphyschem》2009,10(15):2633-2641
Self‐assembled donor/acceptor dyads are of current interest as they are biomimetic to the natural photosynthetic conversion system. Herein, we present an ultrahigh‐vacuum scanning tunneling microscopy and scanning tunneling spectroscopy (UHV‐STM/STS) study of ex situ self‐assembled supramolecular dyads consisting of fulleropyrrolidines (PyC2C60) axially ligated to zinc(II) tetraphenylporphyrin (ZnTPP), self organized on a 4‐aminothiophenol (4‐ATP) self‐assembled monolayer on gold(111). These dyads show both bias‐polarity‐dependent apparent height in STM images and highly rectifying behavior in tunneling spectroscopy. First‐principles density functional theory calculations clarify the conformational and electronic properties of the 4‐ATP/ZnTPP/PyC2C60 system. Interestingly, we find easier tunneling for electrons moving from the acceptor side of the dyads to the donor side, in the inverse‐rectifying sense with respect to previously reported molecular rectifiers. Such behavior cannot be explained as an elastic resonant tunneling process, but it can by using a model based on the Aviram–Ratner mechanism. 相似文献