Porous metal thin films have high potential for use in applications such as catalysis, electrical contacts, plasmonics, as well as energy storage and conversion. Structuring metal thin films on the nanoscale to generate high surface areas poses an interesting challenge as metals have high surface energy. In this communication, we demonstrate direct access to nanostructured metal nanoparticle hybrid thin films with high nanoparticle loadings through spin coating of a mixture of block copolymer and ligand stabilized platinum and palladium nanoparticles. Plasma cleaning to remove the organics results in a conductive metal thin film. We expect that the methods described here can be generalized to other metals, mixtures of metal nanoparticles, and intermetallics.
The π-complexation of an arene to a transition metal center delivers many useful reactivities to the arene moiety. Although synthetic methodologies that take advantage of such π-coordination have mostly been developed as stoichiometric processes, there have been considerable recent advances in the catalytic transformations of aromatic molecules through their activation in the form of transition metal η6-arene complexes. These advances include the π-coordination catalyzed transformations of aryl-heteroatom and side-chain CH and CC bonds and the palladium-catalyzed CH functionalization in pre-formed transition metal η6-arene complexes. This digest paper aims to provide a concise view of these recent advances in the area of transition metal η6-arene complexes. 相似文献
As difunctional compounds containing an ionic bond in the molecule, divalent metal salts (I) of mono(hydroxyethyl) phthalate were prepared in high purity and high yield. Mg and Ca were selected as divalent metal. Metal-containing polyurethanes containing ionic links in the main chain were synthesized by the polyaddition reaction of I or, I–glycols with diisocyanates. The polyurethane obtained were glassy materials or white powders, depending on the species of diisocyanates and glycols. Close agreement between observed and calculated values of metal content of the polyurethanes were obtained. The viscosities (in dimethyl-formamide) of the polyurethanes decreased markedly with increasing of metal content. Moreover, the decomposition temperatures were lowered by introduction of metals into the polyurethanes. However, the decomposition rates of metal-containing polyurethanes were lower than those of polyurethanes not containing metal. 相似文献
Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme. 相似文献
The linear muffin-tin-orbital method is used to calculate the d electron populations of 3d metals in different crystal structures. It is found that valence electronic structure and hence the Kβ/Kα X-ray intensity ratio (R) of a 3d metal changes with the crystal structure. It is concluded that R of a 3d metal depends on the energy band structure rather than the chemical environment. 相似文献
The infinite coordination polymerization…? of metal ions and multitopic organic ligands is explored to fabricate metal–organic micro‐ and nanospheres that can be used as functional matrices. In their Communication on page 2325 ff., D. Maspoch and co‐workers show how this simple process affords spheres that encapsulate active substances, such as magnetic nanoparticles, organic dyes, and quantum dots, to result in multifunctional spheres. Marianne Verdoux is thanked for the cover graphic design.
With their remarkable properties and wide‐ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal‐oxide components. In this review, particular attention is given to core–shell type metal oxide‐coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard.
The cover picture shows a critical review on the organic reactions catalyzed by dinucleating complexes via metal‐metal cooperation. The reaction modes for the catalysis involving late transition metals are including the bimetallic co‐activation of single molecules and dual‐activation of two molecules. More details including the pathways of the metal‐metal cooperation are discussed by Zeng et al. on page 185—201.
Polyaniline‐polypyrrole (PANI‐PPy) nanofibers with high aspect ratios have been synthesized by a one‐step, surfactant‐assisted chemical oxidative polymerization from mixtures of aniline (An) and pyrrole (Py) monomers. PANI‐PPy nanofibers synthesized with an excess of either PANI or PPy show similar spectral (UV‐vis and FT‐IR) characteristics as the individual homopolymers, whereas nanofibers from an equimolar mixture of An and Py display unique spectral characteristics. PANI‐PPy nanofibers undergo a spontaneous redox reaction with metal ions to produce metal nanoparticles with various morphologies and/or sizes. These findings may open new opportunities for synthesizing functional polymer nanofibers and metal nanoparticles with controllable sizes and/or morphologies.
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