聚类卟啉金属配合物*

为模拟天然卟啉所具有的特殊生理活性,结构与性能各异的多种金属卟啉被合成并应用于许多领域。实际上,天然金属卟啉是在特定天然高分子-蛋白质营造的空穴中才能发挥其独特的性质,因此,类卟啉金属配合物的高分子化逐渐受到关注,并在载氧、催化、导电等领域取得重要成果。基于结合方式不同,高分子类卟啉金属配合物可分为高分子担载类卟啉金属配合物与聚类卟啉金属配合物。其中,后者以稳定的类卟啉环作为高分子链,不但使高分子骨架稳定,而且活性中心与类卟啉金属配合物之间有效间隔,同时活性中心相对密集,使其表现出较高的稳定性与活性。线形与平面型聚金属卟啉与金属酞菁表现出良好的导电性与催化活性;手性Salen席夫碱易于聚合得到线形或网状聚Salen希夫碱金属配合物,其表现出较强的催化活性、高ee值和可循环性。异双核聚类卟啉金属配合物也表现出较强的催化活化分子氧性能。     

聚合物键联金属卟啉化合物的合成及其催化性能研究

将卟啉和金属卟啉化合物引入到高分子载体上,不仅仍然保持着卟啉化合物的催化特性,而且还有着聚合物试剂的优良性能。我们     

高分子负载Mn（Ⅲ）卟啉／PhIO体系催化烯烃五氧化反应研究

研究了负载化金属卟啉催化烯烃环氧化反应的催化活性，探索了催化反应体系中轴向配体，溶剂，锰卟啉在高分子上的担载量及反庆温度等对催化反应的影响。结果表明，金属卟啉负载化后，增大了催化剂的稳定性。     

水溶性卟啉及金属卟啉在DNA中的研究进展

近年来, 卟啉及金属卟啉与DNA的相互作用已成为研究的热点. 通过对卟啉及金属卟啉与DNA相互作用的研究将有助于更深地认识DNA本身的结构和功能, 有助于卟啉及金属卟啉在医学上的应用, 对认识很多疾病的治病机制和药物的设计也起到非常重要的作用. 本文阐述了卟啉及金属卟啉与DNA相互作用的方式和影响因素, 并将水溶性卟啉及金属卟啉分为三类: 具有吡啶基或铵基的阳离子型卟啉及金属卟啉, 具有磺酸基或羧基的阴离子型卟啉及金属卟啉, 以及非离子型的卟啉及金属卟啉. 重点论述了这三类水溶性卟啉及金属卟啉与DNA之间的相互作用, 以及这三类水溶性卟啉及金属卟啉在DNA中的应用研究进展.     

键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成及催化烯烃环氧化反应性…

本文研究了键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成，以及在ＣＨ２Ｃｌ２／Ｈ２Ｏ两相体系中催化苯乙烯环氧化反应的性能，探索了催化反应体系中溶液ｐＨ值、ＮａＯＣｌ浓度、轴向配体及相转移催化剂对催化反应的影响。结果说明键联聚乙二醇高分子担载锰（Ⅲ）卟啉是烯烃环氧化反应的一种有效催化剂，其中聚乙二醇链可以络合Ｎａ，使ＯＣｌ富集于金属卟啉周围，起到较好的相转移催化作用。在催化反应的各影响因素中，水相ｐＨ值对     

高分子键联金属卟啉的合成及催化性能

高分子键联金属卟啉的合成及催化性能;高分子担载金属卟啉; 环己烯; 催化氧化     

金属卟啉的直接电化合成及其固体微状安行为研究

用固体微粒伏安法在电极表面直接获得了铜卟啉、铁卟啉及钴卟啉，在氯化钾支持电解质认中用循环安法对meso-四苯基卟啉（Ｈ２ＴＰＰ）及现场合成的金属卟啉的固体电化学行为进行了表征，作为电荷补尝，实验证明在固体金属卟啉还原及氧化过程中同时伴随有钾离子在昌胞中的迁移，文中对金属卟啉的形成机理及其电极反应机理进行了详细探讨。     

高分子负载Mn（Ⅲ）卟啉／PhIO体系催化烯烃环氧化反应研究

研究了负载化金属卟啉催化烯烃环氧化反应的催化活性，探索了催化反应体系中轴向配体、溶剂、锰卟啉在高分子上的担载量及反应温度等对催化反应的影响．结果表明，金属卟啉负载化后，增大了催化剂的稳定性．本文还考察了负载化催化剂对苯乙烯催化环氧化反应的动力学行为，根据Ｍｉｃｈａｅｌｉｓ－Ｍｅｎｔｅｎ方程，求得了相关的动力学参数     

键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成及催化烯烃环氧化反应性能研究

本文研究了键联聚乙二醇高分子担载锰（Ⅲ）卟啉的合成，以及在ＣＨ_２Ｃｌ_２／Ｈ_２Ｏ两相体系中催化苯乙烯环氧化反应的性能．探索了催化反应体系中溶液ｐＨ值、ＮａＯＣｌ浓度、轴向配体及相转移催化剂对催化反应的影响．结果说明键联聚乙二醇高分子担载锰（Ⅲ）卟啉是烯烃环氧化反应的一种有效催化剂，其中聚乙二醇链可以络合Ｎａ，使ＯＣｌ富集于金属卟啉周围，起到较好的相转移催化作用．在催化反应的各影响因素中，水相ｐＨ值对反应的影响最大．     

卟啉组装体的结构、功能和性质

近年来,卟啉及金属卟啉的超分子化学迅速发展成为现代化学的一个重要分支。卟啉及金属卟啉组装体在光、电、纳米等新型功能材料中有广泛的应用,已引起了人们的极大兴趣。本文就卟啉及金属卟啉组装体的功能、性质及应用前景进行了综述。     

Metallorganic side group liquid crystalline polymers containing pi-allylpalladium(II) groups

The preparation and phase properties of some LC pi-allyl and pi-crotyl Pd(II) side group metallorganic polymers and some related salicylaldiminates are described. The LC acrylate functionalized monomers are easily prepared, but their use to obtain the corresponding polymers by radical reaction failed because extensive decomposition of the complexes occurs with the formation of Pd metal. The synthesis of the metallated polymers was therefore performed by reacting the dimeric chloro-bridged organometallic pi-allyl or pi-crotyl Pd(II) complexes with the appropriate ligand polymer which is prepared without difficulties. The organometallic polymers show a nematic mesophase, while the ligand polymer exhibits a smectic A or C phase. Both metallated low molecular mass model compounds and the polymers give stable mesophases, although at lower temperatures compared with the parent ligand compounds.     

Late first-row transition-metal complexes of texaphyrin

The preparation of first-row transition-metal complexes of texaphyrin, a porphyrin-like, monoanionic penta-aza macrocyclic ligand, is reported. Specifically, the synthesis of organic-soluble Mn(II) (1), Co(II) (2), Ni(II) (3), Zn(II) (4), and Fe(III) (5) texaphyrin derivatives and their water-soluble counterparts (6-10) from appropriate metal-free, nonaromatic macrocyclic precursors is described. It was found that metal cations of sufficient reduction potential could act to oxidize the nonaromatic macrocyclic precursor in the course of metal insertion. Complexes were characterized by X-ray diffraction analysis, electrochemistry, flash photolysis, and EPR spectroscopy. The structural and electronic properties of these "expanded porphyrin" complexes are compared with those of analogous porphyrins. Notably, the texaphyrin ligand is found to support the complexation of cations in a lower valence and a higher spin state than do porphyrins. Interactions between the coordinated cation and the ligand pi system appear to contribute to the overall bonding. Texaphyrin complexes of Mn(II), Co(II), and Fe(III) in particular may possess sufficient aqueous stability to permit their use in pharmaceutical applications.     

高分子希夫碱金属配合物的研究进展 (Ⅰ)高分子担载希夫碱金属配合物的制备与性能

综述了近十几年来有关高分子担载希夫碱金属配合物的研究进展。此类配合物所采用的合成方法主要有：（ａ）含乙烯侧基的配体或金属配合物共聚；（ｂ）小分子配体或配合物锚连于高分子载体。其主要性能为结合分子氧和催化活性。     

高分子担载卟啉及其金属络合物研究进展

本文介绍了高分子担载卟啉及其金属络合物在模拟细胞色素Ｐ－４５０，光学灭菌材料，阴离子载体及光敏化学材料等领域的最新研究进展。     

Synthesis, characterization and cation-induced dimerization of new aza-crown ether-appended metalloporphyrins

New metalloporphyrins bearing one or two aryl-aza-crown ether moieties at meso-positions have been synthesized using a palladium catalyzed amination reaction and fully characterized by spectral techniques. X-Ray structural data have been presented for the zinc and copper complexes of mono-substituted aza-crown ether appended metalloporphyrins. UV-Vis and (1)H NMR spectroscopic studies showed that addition of K(+) cations to a solution of monomeric aza-crowned porphyrins in CHCl(3)/MeOH led to cation-induced dimerization of these porphyrins, whereas addition of Na(+) cations yielded a monomeric complex. Axial coordination of the exobidentate ligand (DABCO) to zinc complexes of aza-crowned porphyrins and following binding metal ions led to formation of sandwich complexes with high stability constants.     

Theoretical investigation of one-photon and two-photon absorption properties for multiply N-confused porphyrins

We have theoretically investigated a series of multiply N-confused porphyrins and their Zn or Cu complexes for the first time by using DFT(B3LYP/6-31G*) and ZINDO/SOS methods. The electronic structure, one-photon absorption (OPA), and two-photon absorption (TPA) properties have been studied in detail. The calculated results indicate that the OPA spectra of multiply N-confused porphyrins are red-shifted and the OPA intensities decrease compared to normal porphyrin. The maximum two photon absorption wavelengths lambda(max) are blue-shifted and the TPA cross sections delta(max) are increased 22.7-112.1 GM when the N atoms one by one are inverted from core to beta position to form multiply N-confused porphyrins. Especially delta(max) of N3CP get to 164.7 GM. The electron donors -C6F5s at meso-position can make the TPA cross section delta(max) increase. After forming metal complexes with Cu or Zn, the TPA properties of multiply N-confused porphyrins are further increased except for N3CP, N4CP. Our theoretical findings demonstrate that the multiply N-confused prophyrins as well as their metal complexes and derivatives are promising molecules that can be assembled series of materials with large TPA cross section, and are sure to be the subject of further investigation.     

Main-chain organometallic polymers: synthetic strategies, applications, and perspectives

Main-chain organometallic polymers utilize transition metal-organic ligand complexes as primary components of their backbones. These hybrid materials effectively integrate the physical and electronic properties of organic polymers with the physical, electronic, optical, and catalytic properties of organometallic complexes. Combined with the rich and continuously growing array of ligands for transition metals, these materials have outstanding potential for use in a broad range of applications. This tutorial review discusses the major classes of main-chain organometallic polymers, including coordination polymers, poly(metal acetylide)s, and poly(metallocene)s. Emphasis is placed on their synthesis, characterization, physical properties, and applications, as well as ongoing challenges and limitations. These discussions are supplemented with highlights from the recent literature. The review concludes with perspectives on the current status of the field, as well as opportunities that lie just beyond its frontier.     

meso-四(对烷氧苯基)卟啉及其金属配合物的合成、表征及液 晶性

合成了meso-四(对烷氧苯基)卟啉及其Cu,Co,Zn,Pb金属配合物38个,其中14个为未见文献报道的新化合物。用元素分析,IR,UV,^1HNMR,MS对其进行了表征,确证了其结构。研究了这五个系列化合物的液晶性能,发现16个化合物具有液晶性,探讨了烷氧基链长及配位金属离子对液晶性能的影响。     

Encapsulation of transition metal catalysts by ligand-template directed assembly

Encapsulated transition metal catalysts are presented that are formed by templated self-assembly processes of simple building blocks such as porphyrins and pyridylphosphine and phosphite ligands, using selective metal-ligand interactions. These ligand assemblies coordinate to transition metals, leading to a new class of transition metal catalysts. The assembled catalyst systems were characterized using NMR and UV-vis spectroscopy and were identified under catalytic conditions using high-pressure infrared spectroscopy. Tris-3-pyridylphosphine binds three mesophenyl zinc(II) porphyrin units and consequently forms an assembly with the phosphorus donor atom completely encapsulated. The encapsulated phosphines lead exclusively to monoligated transition metal complexes, and in the rhodium-catalyzed hydroformylation of 1-octene the encapsulation of the catalysts resulted in a 10-fold increase in activity. In addition, the branched aldehyde was formed preferentially (l/b = 0.6), a selectivity that is highly unusual for this substrate, which is attributed to the encapsulation of the transition metal catalysts. An encapsulated rhodium catalyst based on ruthenium(II) porphyrins and tris-meta-pyridyl phosphine resulted in an even larger selectivity for the branched product (l/b = 0.4). These encapsulated catalysts can be prepared easily, and various template ligands and porphyrins, such as tris-3-pyridyl phosphite and ruthenium(II) porphyrins, have been explored, leading to catalysts with different properties.