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1.
Frdrique Brgier Vincent Sol Yves Champavier Laurent Galmiche Clmence Allain Pierre Audebert 《Molecules (Basel, Switzerland)》2022,27(19)
We have prepared the first example of a porphyrin linked to an heptazine photoactive antenna. The two entities, linked with an alkyl spacer, demonstrate the activity of both active moieties. While they behave electrochemically independantly, on the other hand the spectroscopy shows the existence of energy transfer between both partners. 相似文献
2.
Weilin Chen Yangguang Li Dr. Yonghui Wang Enbo Wang Prof. Dr. Zhiming Zhang 《无机化学与普通化学杂志》2009,635(11):1678-1687
Employing a “one‐pot” synthesis strategy, the reaction of Na2WO4·2H2O, Na2HAsO4·7H2O, FeCl3·6H2O, various Ln3+ ions, and hexamethylenetetramine (HMTA) in aqueous solutions with pH values ranging from 5.5 to 6.5 results in the isolation of polytungstoarsenate‐based iron aggregates, ‐K8Na14[HMTA]4[(FeIII3FeII0.25(OH)3)(AsO4)(AsW9O34)]4·24H2O ( 1 ) (HMTA = hexamethylenetetraamine). The polyoxoanion of 1 contains a mixed‐valent {FeIII12FeII(μ3‐OH)12(μ4‐AsO4)4} cluster surrounded by four [B‐α‐AsW9O34]9? units. It is the first polytungstatoarsenate‐based mixed‐valent {FeIII12FeII} aggregate and the largest iron cluster based on [AsW9O34]9? ligands. The compound was characterized by elemental analyses, IR, UV/Vis absorption, and diffuse‐reflectance UV/Vis spectroscopy, TG analyses, XRPD, XPS and gel‐filtration chromatography. The electrochemical and electrocatalytical properties were also investigated. Crystal data for 1 , orthorhombic, Fddd, a = 28.156(6) Å, b = 36.003(7) Å, c = 42.126(8) Å, α = 90°, β = 90°, γ = 90°, Z = 8. 相似文献
3.
卟啉及其衍生物合成进展 总被引:4,自引:0,他引:4
按卟啉母核的不同合成方法,介绍了卟啉衍生物的合成进展。从各种小分子的缩合而合成卟啉的方法包括经典的Alder-Long法、Lindsey法和新颖的[2+2]法、[3+1]法。这些方法能够合成许多结构复杂的卟啉。对卟啉大分子进行β-、meso-位功能团的引入,有卤代、硝化、甲酰化等,并能进一步转化成其它功能团。 相似文献
4.
The electrochemistry of metallomacrocycles is known to depend on a variety of factors, some of which are related to the nature
of the macrocycle, some to the central metal ion and some to the solution conditions. This present paper presents a brief
overview of metalloporphyrin and metallocorrole redox reactivity while outlining the most important structural factors which
influence the reversible half-wave potentials for oxidation or reduction of these complexes in non-aqueous media.
Electronic Publication 相似文献
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Aixiang Tian Zhangang Han Jun Peng Prof. Dr. Jiangli Zhai Yulong Zhao 《无机化学与普通化学杂志》2007,633(3):495-503
An inorganic‐organic hybrid solid (H6/5bppy)5[P2W18O62]·4.5H2O ( 1 ) (bppy = 4‐(5‐(4‐bromophenyl)pyridin‐2‐yl)pyridine) was hydrothermally synthesized by using pre‐constructed Wells‐Dawson type salt α‐K6P2W18O62·15H2O as inorganic moiety. The crystal structure keeps integrated and steady under the interactions together of aryl packing, hydrogen bonding and halogen bonding. X‐ray single crystal structure analysis reveals that compound 1 contains cavities with the sizes of about 6 × 8Å, in which H2O molecules are captured. The hybrid was used as a solid bulk modifier to fabricate a three‐dimensional bulk‐modified carbon paste electrode ( 1 ‐CPE) by direct mixing. The electrochemical and electrocatalytic behavior of the 1 ‐CPE has been studied in detail. The results exhibit that the redox ability of the Wells‐Dawson polyanions can be maintained in the hybrid solid, which has a good electrocatalytic activity toward the reduction of bromate and hydrogen peroxide. A hydrodynamic voltammetric experiment was performed to characterize the electrode as an amperometric sensor for the determination of hydrogen peroxide. The 1 ‐CPE showed long‐term stability and excellent reproducibility of surface renewal. 相似文献
7.
Porphyrins with fluorenyl and fluorenone groups at the meso-positions have been synthesized and characterized, and the fluorescence of these compounds has been studied. Following selective excitation of the pendant arms with UV light, we show that the energy is transferred to the porphyrin core and reemitted as red light. In comparison to tetraphenylporphyrin, the luminescence properties are markedly improved. The fluorescence quantum yields of tetrafluorenylporphyrin 1 and tetrafluorenoneporphyrin 2 are 0.22 and 0.25, respectively. 相似文献
8.
铜(Ⅱ)、镍(Ⅱ)的新卟啉配合物的SERRS谱及DNA的影响周光明,盛蓉生,熊亚,徐知三,王小华,曾云鹗(武汉大学化学系、分析测试中心,武汉,430072)关键词SERRS,卟啉,DNA从分子水平上认识卟啉的生物学过程一直是人们感兴趣的研究领域,表面... 相似文献
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There is substantial recent interest worldwide in the construction of multiporphyrin assemblies which can either mimic naturally occurring multichromophore aggregates, such as the photosynthetic reaction center and the light harvesting complex of purple bacteria, or which can be used as electron- and/or energy-transfer molecular devices for advanced technological tasks. The metal-mediated self-assembly approach, which exploits the formation of coordination bonds between peripheral basic site(s) on the porphyrins and metal centers, has recently allowed the design and preparation of sophisticated supramolecular architectures whose complexity and function begin to approach the properties of naturally occurring systems. Within this framework, meso -pyridyl/phenyl porphyrins (PyPs), or strictly related chromophores, can provide geometrically well-defined connections to as many as four metal centers by coordination of the pyridyl groups. Several discrete assemblies of various nuclearities, in which the pyridylporphyrins are linkers binding metalloporphyrins and/or coordination compounds, have been constructed in recent years. Our contribution to this field is reviewed, with the aim of providing insight into the design of new, more elaborated architectures of higher order. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(5):567-579
We report the crystal structure of dimeric precursor Na12[(Na(H2O)2)6(α-BiW9O33)2] (1), and the interaction of this precursor with transition metal ions. Interaction of 1 with Cu2+ in neutral medium leads to the formation of a Hervé-type sandwich polyoxoanion [(Cu(H2O))3(α-BiW9O33)2]12? (2) in high yield. Interaction of 1 with M2+ (M?=?Zn, Ni, Co, Mn) in acidic aqueous medium leads to formation of Krebs-type sandwich polyoxoanions [(M(H2O)3)2(WO)2(β-BiW9O33)2]10? (3–6). Coordination geometry of the M2+ ions, counterions and precursors can affect the structure of products. In our experiments, only the interaction of 1 with Cu2+ forms a trisubstituted sandwich-type product. The method using [α-BiIIIW9O33]9? as starting material is a convenient and effective route for the synthesis of sandwich-type tungstobismutates in high purity and yield. The electrochemical properties of these sandwich-type tungstobismutates in aqueous solution are described. 相似文献
12.
Jingjing Zhi Xueying Xu Sijie Duan Dr. Weilin Chen Fengrui Li Dr. Xiangwei Guo Yinan Hou 《欧洲无机化学杂志》2023,26(4):e202200599
The dependence of perovskite-based photovoltaic devices on toxic solvents limits their applications. Therefore, we added polyoxometalates into ionic liquids, as the green solvent and polyoxometalates synergistically improve the performance of devices. Firstly, methylammonium formate (MAFa) as solvent delayed the crystallization process of perovskite thin films, thus obtained an extended crystal domain, and the photocurrent of the device was increased from 35.51 μA to 63.18 μA. Secondly, introducing PW12 into this green solvent system, the matched energy level and good electron transmission rate promoted the separation of photogenerated excitons and accelerated the transmission of photogenerated electrons in perovskite. After dual adjustment of MAFa and PW12, the photocurrent of the champion device reached 95.99 μA (about 2.7 times of the original device), the unpacked devices can still maintain 80 % of initial value after being placed under environmental conditions for 700 h. 相似文献
13.
卟啉及其类似物超分子功能的分析应用 总被引:17,自引:2,他引:17
应用超分子化学的理论和研究成果解决分离、分析与有关理论问题是现代分析化学的一个重要方面。评述了卟啉及其金属配合物、类似物的分子识别、组装和仿生催化作用及其在生物相关物质的色谱分离分析,各类传感器、模拟酶分析等方面的应用研究进展,也展望了发展趋势。引用文献86篇。 相似文献
14.
7种中位—四取代苯基卟啉化合物的合成 总被引:3,自引:0,他引:3
卟啉是一类结构与生命物质(如血红素和维生素B_(12))相似的化合物,近年来曾被用于人体肿瘤的光动力学治疗;此外,在电化学、光物理学和光化学、放射医学、微量元素测定、纺织品漂洗等领域中的应用也相当广泛,已受到科技工作者的普遍关注和重视。本文按Rothemond法将相应的取代苯甲醛与新蒸吡咯在丙酸中缩合,制得具有酸性、中性和碱 相似文献
15.
《Journal of Coordination Chemistry》2012,65(1-3):99-104
Abstract Novel tripyrrane macrocycles have been prepared by the Schiff base condensation of 2,5-bis-(3-ethyl-5-formyl-4-methyl-pyrrol-2-ylmethyl)-3,4-diethylpyrrole and simple diamines. The structurally characterized macrocycle 1 forms 1:1 complexes with both Rh(I) and Zn(II) cations in which the metal is coordinated only to the imine nitrogens. In the presence of Cd(II) and oxygen, however, compound 1 is oxidized to the aromatic pentadentate ‘expanded porphyrin’ macrocycle 5, into which the metal cation is fully complexed. 相似文献
16.
Alberto Credi Steven J. Langford Anna Prodi J. Fraser Stoddart Margherita Venturi 《Supramolecular chemistry》2013,25(2):303-311
Abstract The spectroscopic and electrochemical properties of two cyclophanes containing one and, respectively, two 2,7-diazapyrenium electron-acceptor units, and of their [2]catenanes with macrocycles containing two dioxybenzene or dioxynaphthalene electrondonor units have been investigated. The absorption spectra of the catenanes show weak and broad bands in the visible region, assigned to charge-transfer (CT) interactions. The very strong and structured fluorescence (298 K) and the structured fluorescence and phosphorescence (77 K) of the diazapyrenium unit are maintained in the two cyclophanes, but they are no longer present in the [2]catenanes, presumably because of a quenching process caused by the lower energy CT excited states. Each diazapyrenium unit undergoes two distinct reduction processes - only the first one of which is fully reversible - that are hardly affected at all when the diazapyrenium units are incorporated in a cyclophane. In the [2]catenanes, the CT interaction displaces the reduction processes of the diazapyrenium units toward more negative potentials. The results obtained for the diazapyrenium and previously investigated 4,4′-bipyridinium salts, selected cyclophane derivatives, and some [2]catenanes obtained by interlocking the cyclophanes with macrocycles containing two dioxyaromatic electron-donor units are compared and discussed. 相似文献
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Inorganic metal–oxygen cluster anions form a class of compounds that is unique in its topological and electronic versatility and is important in several disciplines. Names such as Berzelius, Werner, and Pauling appear in the early literature of the field. These clusters (so-called isopoly- and heteropolyanions) contain highly symmetrical core assemblies of MOx units (M = V, Mo, W) and often adopt quasi-spherical structures based on Archimedean and Platonic solids of considerable topological interest. Understanding the driving force for the formation of high-nuclearity clusters is still a formidable challenge. Polyoxoanions are important models for elucidating the biological and catalytic action of metal–chalcogenide clusters, since metal–metal interactions in the oxo clusters range from very weak (virtually none) to strong (metal–metal bonding) and can be controlled by choice of metal (3d, 4d, 5d), electron population (degree of reduction), and extent of protonation. Mixed-valence vanadates, in particular, show novel capacities for unpaired electrons, and the magnetic properties of these complexes may be tuned in a stepwise manner. Many vanadates also act as cryptands and clathrate hosts not only for neutral molecules and cations but also for anions, whereby a remarkable “induced self-assembly process” often occurs. Polyoxometalates have found applications in analytical and clinical chemistry, catalysis (including photocatalysis), biochemistry (electron transport inhibition), medicine (antitumoral, antiviral, and even anti-HIV activity), and solid-state devices. These fields are the focus of much current research. Metal–oxygen clusters are also present in the geosphere and possibly in the biosphere. The mixed–valence vanadates contribute to an understanding of the extremely versatile geochemistry of the metal. The significant differences between the chemistry of the polyoxoanions and that of the thioanions of the same elements is of relevance to heterogeneous catalysis, bioinorganic chemistry, and veterinary medicine. 相似文献
19.
Archismita Misra Karoly Kozma Carsten Streb May Nyman 《Angewandte Chemie (International ed. in English)》2020,59(2):596-612
Polyoxometalates (POMs) are molecular metal‐oxide anions applied in energy conversion and storage, manipulation of biomolecules, catalysis, as well as materials design and assembly. Although often overlooked, the interplay of intrinsically anionic POMs with organic and inorganic cations is crucial to control POM self‐assembly, stabilization, solubility, and function. Beyond simple alkali metals and ammonium, chemically diverse cations including dendrimers, polyvalent metals, metal complexes, amphiphiles, and alkaloids allow tailoring properties for known applications, and those yet to be discovered. This review provides an overview of fundamental POM–cation interactions in solution, the resulting solid‐state compounds, and behavior and properties that emerge from these POM–cation interactions. We will explore how application‐inspired research has exploited cation‐controlled design to discover new POM materials, which in turn has led to the quest for fundamental understanding of POM–cation interactions. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(21):3814-3824
Three compounds, [AsMo8V6O42][Cu(2,2?-bpy)2]2[Cu(2,2?-bpy)]·4H2O (1), [PMo8V6O42][Cu(2,2?-bpy)2]2[Cu(2,2?-bpy)]·3H2O (2) and [PMo8V6O42][Cu(2,2?-bpy)2]2[Cu(2,2?-bpy)]·3.5H2O (3), have been synthesized under hydrothermal conditions and characterized by IR, UV–vis, XRD, TG, elemental analysis, and X-ray diffraction analysis. Single-crystal X-ray structure analysis reveals that 1 and 2 are isostructural and isomorphous, whereas 2 and 3 are polymorphs. Polymorphs of 1 have not been synthesized yet. The mixed-valent transition metal ion in 1–3 has been further confirmed by TG analyses. Catalytic properties of 1 and 2 have also been studied. 相似文献