Synthesis of Polyoxometalate−Polymer Hybrid Polymers and Their Hybrid Vesicular Assembly

Han, Yaokun; Yu, Xiao; Zhang, Zijian; Liu, Bo; Zheng, P.; He, Suqin; Wang, Wei

doi:10.1021/ma9011686

Cited by 124 publications

(98 citation statements)

References 38 publications

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“…[35] Other materials, such as polyoxometalate anionic metal-oxygen nanocages, have been successfully attached to polymer tethers via covalent bonds. [36,37] As these studies demonstrate, a wide range of materials are amenable to this type of modification and are experimentally accessible, opening up an enormous design space for new functional materials.…”

Section: Tethered Np Building Blocksmentioning

confidence: 99%

Rational design of nanomaterials from assembly and reconfigurability of polymer-tethered nanoparticles

2015

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Polymer-based nanomaterials have captured increasing interest over the past decades for their promising use in a wide variety of applications including photovoltaics, catalysis, optics, and energy storage. Bottom-up assembly engineering based on the self-and directed-assembly of polymer-based building blocks has been considered a powerful means to robustly fabricate and efficiently manipulate target nanostructures. Here, we give a brief review of the recent advances in assembly and reconfigurability of polymer-based nanostructures. We also highlight the role of computer simulation in discovering the fundamental principles of assembly science and providing critical design tools for assembly engineering of complex nanostructured materials.

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Section: Tethered Np Building Blocksmentioning

confidence: 99%

Rational design of nanomaterials from assembly and reconfigurability of polymer-tethered nanoparticles

2015

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“…13 The proton salts of the obtained POM-PS composite formed aggregates in DMF, which showed a transition from vesicles to tubular structures upon thermal annealing, these latter being thermodynamically more stable. 14 To the best of our knowledge very few stimuli-responsive covalent POM-polymer hybrids have been studied so far.…”

mentioning

confidence: 96%

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Haye

Costa

Pembouong

et al. 2015

Polymer

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ABSTRACT. In this article, we study the temperature-induced phase transition of aqueous solutions of tailor-made Dawson polyoxometalate-poly(N,N-diethylacrylamide) hybrids (POMPDEAAm) by means of differential scanning calorimetry, dynamic light scattering and cryo-TEM microscopy. Generally, the typical thermoresponsive aggregation of the PDEAAm in water was transferred to the hybrids. The organization of the compounds in solution below and above the transition temperature was studied, and precious insights in the aggregation mechanisms were obtained. The impact of the polymer chain-ends, the nature of the counterions of the negatively charged POM subunits and the weight fraction of the POM was elucidated, revealing a strong influence of the POM's counter-ions. Temperature and nature of the cations are thus two external factors that can be used to control the properties of the conjugates.

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“…将它们通过共价键与有机分子 [9,12～15] 、线性聚合物 [10,11] 、寡聚物 [16] 等结合制备了一系列有趣的称为形状两亲性分子(Shape Amphiphiles). 很明显两个构筑单元在拓扑结构上存在明显的差异.…”

Section: 多金属氧簇(Poms)unclassified

Synthesis and Self-Assembled Structure of A Cluster-Cluster Hybrid Molecule Composed of POM and POSS Clusters

Hou¹,

Minbiao²,

Wang³

2014

Acta Chim. Sinica

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Polyhedral oligosilsesquioxane (POSS) and polyoxometalate (POM) are two kinds of clusters having totally different physical and chemical properties. For instance, the POSS cluster dissolves in weakly polar solvents, such as toluene, while the POM cluster, encapsulated by tetrabutylammonium counterions, dissolves in strongly polar solvents, such as acetonitrile, meaning the strong incompatibility. Based on this reason and their fixed shape, a novel cluster-cluster hybrid molecule with a V-shaped molecular structure (POM-2POSS) was rationally designed by covalently linking the two POSS clusters on the one side of the POM cluster. In the experiment, a two-azido-containing organosilyl derivative of a Wells-Dawson-type POM cluster and a one-propargyl-containing derivative of a POSS cluster were prepared at first. Then, the cluster-cluster hybrid was successfully synthesized by Cu-catalyzed click reaction between the two azide groups in the one POM derivative and the two propargyl groups in the two POSS derivatives. The chemical structure of this hybrid molecule was carefully characterized by NMR, ESI-MS and IR. In view of their strong incompatibility and of the particular three-dimensional (3D) structure POM-2POSS was expected to be able to self-assemble into ordered supramolecular structures. In the sample preparation POM-2POSS was dissolved in acetonitrile with a concentration of 5 mg/mL, and then the solution was dropped onto silicon substrates to prepare the thin film samples, finally the thin film samples were annealed in an acetonitrile vapor for 14 d. The film on the silicon substrate was characterized by XRD. The thin film samples for TEM characterization were made at first by floating onto the water surface and then transferred onto copper mesh. The structural analyses clearly demonstrated that the hybrid molecule self-assembled into a highly ordered lamellar morphology with a 5.1 nm periodicity, smaller than those found in block copolymers with a similar molecular weight. Formation of the highly ordered morphology reflects a self-assembly process due to absence of intermolecular entanglements, while the sub-5 nm periodicity is because of the 3D structures of the two building blocks. The findings provide a new platform for understanding of the self-assembly of nano-clusters and for development of novel hybrid materials.

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Synthesis of Polyoxometalate−Polymer Hybrid Polymers and Their Hybrid Vesicular Assembly

Cited by 124 publications

References 38 publications

Rational design of nanomaterials from assembly and reconfigurability of polymer-tethered nanoparticles

Rational design of nanomaterials from assembly and reconfigurability of polymer-tethered nanoparticles

Study of the temperature-induced aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

Synthesis and Self-Assembled Structure of A Cluster-Cluster Hybrid Molecule Composed of POM and POSS Clusters

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