共查询到19条相似文献,搜索用时 93 毫秒
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金属-超分子聚合物是由金属离子与配体之间的相互作用形成的,是一类具有多样化几何构造和拓扑结构的新型功能高分子,它包括线型、接枝、交联、树枝等多种骨架结构.金属-超分子聚合物具有光、电、磁等特性,因此潜在的应用前景非常广阔,不仅可以在生物医用、分子器件、纳米材料,还可以在催化化学反应及吸附储氢等领域获得应用.由于吡啶基团为常用配体,且近年含吡啶基团的金属-超分子聚合物研究最为广泛,最为代表性,因此,本文以聚合物结构分类对近几年含吡啶基团的金属-超分子聚合物的研究进展作了简要综述. 相似文献
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多重氢键超分子聚合物 总被引:1,自引:0,他引:1
超分子聚合物是通过单体单元间的可逆非共价作用(包括氢键、π-π相互作用和金属配位作用等)形成的,由于非共价键的方向性和强度,这类聚合物显示了许多有趣的功能,例如刺激响应性和纳米结构自组装.本文总结了近三年来多重氢键超分子聚合物在改善聚合物性能、形成复杂分子构造、自组装纳米结构等方面的作用,并对超分子聚合物的应用进行了展... 相似文献
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将金属配位和主客体相互作用引入到同1个超分子体系中,设计合成了2个超分子单体1和2.通过这2个超分子单体分级自组装形成的交联网状超分子聚合物构建了一种多重刺激响应性和良好自修复性能的超分子凝胶.同时,进一步将具有聚集诱导发光性能的四苯乙烯引入到这种超分子体系中,以赋予超分子体系新颖的发光性能.单体分子1是由中间为双苯并24-冠-8的冠醚连接2个四苯基乙烯荧光生色团,两端为2个三联吡啶分子构成的1个主体分子.单体分子1两端的三联吡啶基团可以与过渡金属Zn(OTf)2进行金属配位形成线型超分子聚合物3;而中间的冠醚基团与双二级铵盐客体分子2通过主客体相互作用进一步形成交联超分子聚合物4.当该交联超分子聚合物的浓度达到30 mmol/L时,可形成荧光超分子聚合物凝胶.通过核磁共振(1H-NMR和DOSY)与黏度等测试方法,证明了线形和交联超分子聚合物的形成,并进一步通过流变的测试证明了超分子聚合物凝胶的形成及其良好的自修复性能.除此之外,由于引入的主客体相互作用以及金属配位固有的刺激响应性,该荧光超分子聚合物凝胶表现出对温度、p H值、K+离子和竞争配体的刺激响应性能. 相似文献
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本文介绍了近几年来一个热门的研究领域-纳米超分子笼和具有纳米孔洞的金属-有机聚合物的研究现状和发展趋势。目前该领域的研究主要集中在:设计合成有机桥联配体并与金属离子自组装成各类具有纳米孔洞的超分子化合物和一维、二维或三维的金属-有机聚合物,应用结构化学研究手段,研究它们的自组装规律、空间结构、电子结构及其物理化学性能,寻找这两类化合物在生物工程与功能材料等领域中的应用。 相似文献
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总结了近年来在水溶性三维超分子聚合物、 超分子有机框架、 超分子-金属有机框架杂化结构、 超分子-共价-金属有机框架杂化结构及共价有机框架合成、 催化和输送功能方面的研究进展, 指出了有序三维聚合物未来研究面临的挑战并展望今后的发展方向. 相似文献
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The use of metal ion-induced polymerizations of a ditopic ligand offers a facile route to the preparation of organic/inorganic hybrid materials. Such metallo-supramolecular polymers potentially offer the functionality of the metal ion along with the processibility of a polymer. We report, herein, the preparation of gellike metallo-supramolecular polymers prepared from a monomer unit, which consists of a 2,6-bis-(benzimidazolyl)-4-hydroxypyridine unit attached to either end of a polyether chain, mixed with a transition metal ion (e.g., Co(II) or Zn(II)) and a small percentage of a lanthanoid metal (e.g., La(III), Eu(III)). Such materials show dramatic reversible responses to a variety of stimuli, including thermal, mechanical, chemo, and photo. The nature of the response can be controlled by the nature of the combination of transition metal ion and lanthanide metal ion used. 相似文献
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Four novel fully π-conjugated α,ω-bis(terpyridine)oligothiophenes characterized by NMR, IR, and HR-mass spectroscopy are presented and their electronic absorption/emission and redox properties are described based on both experiments and theoretical calculations. These compounds can be potentially utilized as building blocks for preparation of conjugated metallo-supramolecular polymers or dynamers and related functional materials. 相似文献
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Metal ion coordination in metallo-supramolecular assemblies offers the opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. In particular, dynamic coordination polymers offer exciting opportunities to provide materials with responsive properties. In addition, this approach allows to incorporate the well known properties of metal complexes in polymeric architectures. This review highlights the improvements and the possible applications based on metallo-supramolecular systems with an emphasis on materials science. Examples for new materials such as molecular magnets, coordination polymers as carrier package as well as molecular electronics are featured in this article. 相似文献
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Lavalette A Hamblin J Marsh A Haddleton DM Hannon MJ 《Chemical communications (Cambridge, England)》2002,(24):3040-3041
Metallo-supramolecular diiron(II) triple-helical cores based on pyridylimine ligands and decorated with acrylate or methacrylate units are copolymerised with methyl methacrylate (MMA) as major comonomer using AIBN. 相似文献
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Thermo-, photo-, and chemo-responsive shape-memory properties from photo-cross-linked metallo-supramolecular polymers 总被引:2,自引:0,他引:2
Films exhibiting multiresponsive shape-memory properties have been accessed using covalently cross-linked metallo-supramolecular polymers. Low molecular weight poly(butadiene) was end-capped with 4-oxy-2,6-bis(N-methylbenzimidazolyl)pyridine (-OMebip) ligands that upon addition of metal salts spontaneously formed high molecular weight metallo-supramolecular polymers. The addition of a tetra-functional thiol along with a photoinitiator results in mechanically stable films via solution-casting. These films consist of a soft poly(butadiene) phase and a hard metal-ligand phase. Photo-cross-linking of the poly(butadiene) soft phase, via the thiol-ene reaction, upon exposure to relatively low intensity light, allows access to a diverse range of permanent shapes. Investigations into the temporary shape fixing and recovery of these materials were undertaken to determine the effects of cross-link density and the nature of the metal salts. The key component in fixing and releasing the temporary shape is the metal-ligand hard phase, and as such any stimulus that can disrupt this phase (light, heat, or chemicals) can be used to create the temporary shape and induce its recovery back to the permanent shape. 相似文献
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Hannon MJ Painting CL Plummer EA Childs LJ Alcock NW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(10):2225-2238
Multiple competing molecular interactions (metal-ligand, pi-stacking and hydrogen-bonding) in the silver(I) complexes of 4'-thiomethyl-2,2':6',2"-terpyridine give rise to a range of different molecular architectures, in which the metal-ligand coordination requirements are satisfied in quite different ways. Polynuclear supramolecular spirals, aggregated mononuclear and aggregated dinuclear units are all structurally characterised. The metallo-supramolecular architecture obtained displays a remarkable dependence both on the choice of non-coordinated anion and the type of solvent used (coordinating or non-coordinating). The anion dependence is particularly surprising, since the anions are not integrated into the centre of the supramolecular structure. The solution behaviour is also solvent and anion dependent, with aggregation of planar mononuclear cations observed in acetonitrile, but oligonuclear spiral species implicated in nitromethane. The extraordinarily variable geometries of these systems suggest that they provide a novel example of the "frustration" principle, in which opposing tendencies cannot simultaneously be satisfied and identify an alternative approach to the design of metallo-supramolecular systems whose structure is responsive to external agents. 相似文献
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《Tetrahedron》2019,75(28):3809-3814
Two types of optical active metallo-supramolecular polymers were successfully constructed from the complexation of two enantiopure bis-pyridine-dioxazole (bis-pybox) ligands and 3d transition metal ions such as Zn2+ and Fe2+ in organic solution. The self-assembly process was investigated via UV–vis and fluorescent titration. The chiral characteristic of polymers was detected by circular dichroism. It was revealed that the phenyl-substituted polymers showed higher stability than the benzyl-substituted ones. Temperature-dependent circular dichroism spectra demonstrated the dynamic structure of this type polymer under the variation of temperature. This work highlights the opportunity in designing and constructing of the optical active metallo-supramolecular polymers from the organic privilege ligands in the field of asymmetric catalysis. 相似文献
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Pascu M Tuna F Kolodziejczyk E Pascu GI Clarkson G Hannon MJ 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1546-1555
Aggregation of metallo-supramolecular architectures through additional coordination is explored by introducing metal-binding units onto the outside of the supramolecular architectures. This is achieved within the framework of our imine-based approach to supramolecular architecture, by replacing the pyridylimine units with pyrazylketimine units. An advantage of the design is that it retains the ease-of-synthesis which characterises our imine-based approach. Silver(I) complexes of three pyrazylketimine ligand systems are described. The complexes demonstrate that introducing pyrazine donor units does indeed allow higher-order assembly of the distinct supramolecular architectures into engineered coordination polymers. Two distinct types of aggregation are observed. In the first, the donors on the outside of one architecture bind to the metals of another to link the units into a polymeric array. In the second type, the donors on the outside of the architectures bind to separate metal centres which are themselves not part of the architectures, and these separate metal centres link the units to form the macromolecular array. The weaker donor nature of the pyrazine nitrogens (compared to pyridine) also introduces an additional element into the design; higher coordination numbers are favoured and this can lead to arrays with higher connectivity than those observed in the discrete pyridylimine architectures. 相似文献
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AbstractTwo novel building blocks M1, M2 with different electronic structures, were synthesized based on 2,2′:6′,2″-terpyridine modified with cyano-p-phenylenevinylene (CN-PV) and carbazole moieties through Knoevenagel condensation and Suzuki coupling, respectively. Directed by transition metal ion Zn2+, the metallo-homopolymers P1, P2 and metallo-copolymer P3 were obtained via self-assembly polymerization. The structures of the monomers and metallo-supramolecular polymers were fully characterized by MS, 1H-NMR and 13C-NMR. Meanwhile, the UV–vis absorption, photoluminescence (PL) and electrochemical properties of these compounds were systematically investigated. With respect to that of the monomers, both the UV–vis absorption and PL spectra of the polymers are significantly red-shifted. The resulting metallo-supramolecular polymers show similar double absorption peaks (342, 418?nm for P1, 339, 410?nm for P2, and 332, 412?nm for P3), which is caused by the π–π* transition and intramolecular charge transfer (ICT). Further, all the polymers display red-orange emission in toluene and narrow electrochemical energy gaps of 1.46, 1.65 and 1.48?eV for P1, P2, and P3, respectively. 相似文献