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showing 10 items of 30 documents
Towards Atomically Precise Supported Catalysts from Monolayer‐Protected Clusters: The Critical Role of the Support
2020
Abstract Controlling the size and uniformity of metal clusters with atomic precision is essential for fine‐tuning their catalytic properties, however for clusters deposited on supports, such control is challenging. Here, by combining X‐ray absorption spectroscopy and density functional theory calculations, it is shown that supports play a crucial role in the evolution of monolayer‐protected clusters into catalysts. Based on the acidic nature of the support, cluster‐support interactions lead either to fragmentation of the cluster into isolated Au–ligand species or ligand‐free metallic Au0 clusters. On Lewis acidic supports that bind metals strongly, the latter transformation occurs while pre…
Worldwide Scientific Research on Nanotechnology: A Bibliometric Analysis of Tendencies, Funding, and Challenges
2020
[EN] The main objective of this investigation was to analyze the scientific production in global research on nanotechnology, integrating scientific production, funding of studies, collaborations between countries, and the most cited publications. The source for obtaining the research papers for our analysis was the Science Citation Index Expanded from the Web of Science. A total of 3546 documents were extracted during the period of 1997-2018. Food science & technology, chemistry (applied and analytical), spectroscopy, and agriculture appeared as the main areas where the articles were published. Most prolific and cited journals were Analytical Methods, Journal of Agricultural and Food Chemis…
Endohedral Mixed Aggregates: Sodium Alkoxide Cages with Organic or Inorganic Central Anions and Variable Hull.
2021
Abstract Alkali metal alkoxides are widely used in chemistry due to their Brønsted basic and nucleophilic properties. Potassium alkoxides assist alkyllithium in the metalation of hydrocarbons in Lochmann‐Schlosser‐bases. Both compounds form mixed aggregates, which enhance the thermal stability, solubility, and the basic reactivity of these mixtures. A very unusual spherical mixed alkoxy aggregate was discovered by Grützmacher et al., where a central dihydrogen phosphide anion is surrounded by a highly dynamic shell of thirteen sodium atoms and a hull of twelve tert‐butoxide groups. This structural motif can be reproduced by a reaction of trimethylsilyl compounds of methane, halogens, or pse…
Synthesis, Thermal, and Optical Properties of Tris(5‐aryl‐1,3,4‐oxadiazol‐2‐yl)‐1,3,5‐triazines, New Star‐Shaped Fluorescent Discotic Liquid Crystals
2019
Abstract The synthesis of tris(aryloxadiazolyl)triazines (TOTs), C 3‐symmetrical star‐shaped mesogenes with a 1,3,5‐triazine center, 5‐phenyl‐1,3,4‐oxadiazole arms, and various peripheral alkoxy side chains is reported. Threefold Huisgen reaction on a central triazine tricarboxylic acid and suitable aryltetrazoles yields the title compounds. Selected analogues with a benzene center are included in this study and allow for an evaluation of the impact of the central unit on the physical properties. Thermal (differential scanning calorimetry, DSC; polarization optical microscopy, POM), optical (UV/Vis, fluorescence), electric (time of flight, TOF), and structural (single crystal; wide‐angle X‐…
Filling the Gap in the Metallacrown Family: The 9‐MC‐3 Chromium Metallacrown
2021
Abstract In this work, we report on a long‐sought missing complex in the metallacrown family. We synthesized and characterized the novel chromium metallacrown (MC) complex {CrIII(μ 2‐piv)3[9‐MCCr(III)N(shi)‐3](morph)3}⋅MeOH (in which shi3−=salicyl hydroxamate, piv=pivalate, and morph=morpholine). The MC with a 9‐MC‐3 cavity of kinetically inert chromium(III) ions was synthesized by a solvothermal reaction. Magnetization measurements reveal a high spin ground state.
Influencing the Self‐Sorting Behavior of [2.2]Paracyclophane‐Based Ligands by Introducing Isostructural Binding Motifs
2020
Abstract Two isostructural ligands with either nitrile (Lnit) or isonitrile (Liso) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself (Lnit) or its precursors (Liso) were resolved by HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental electronic circular dichroism (ECD) spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf)2] differ in their composition: whereas Lnit forms dinuclear complexes, Liso…
Reactivity of Nickel(II) Porphyrins in oCVD Processes—Polymerisation, Intramolecular Cyclisation and Chlorination
2019
Abstract Oxidative chemical vapour deposition of (5,15‐diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di‐ to tri‐ and tetraphenyl substitution. DFT calculations support the proposed radical oxi…
Dehydrogenative Anodic C−C Coupling of Phenols Bearing Electron‐Withdrawing Groups
2019
Abstract We herein present a metal‐free, electrosynthetic method that enables the direct dehydrogenative coupling reactions of phenols carrying electron‐withdrawing groups for the first time. The reactions are easy to conduct and scalable, as they are carried out in undivided cells and obviate the necessity for additional supporting electrolyte. As such, this conversion is efficient, practical, and thereby environmentally friendly, as production of waste is minimized. The method features a broad substrate scope, and a variety of functional groups are tolerated, providing easy access to precursors for novel polydentate ligands and even heterocycles such as dibenzofurans.
A Next‐Generation Air‐Stable Palladium(I) Dimer Enables Olefin Migration and Selective C−C Coupling in Air
2020
Abstract We report a new air‐stable PdI dimer, [Pd(μ‐I)(PCy2 tBu)]2, which triggers E‐selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C−C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C−Br, C−OTf/OFs, and C−Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous PdI dimer generations for substrates that bear substituents ortho to C−OTf.
Renewable energies: Worldwide trends in research, funding and international collaboration
2019
The main aim of this study was to analyse scientific and energy production, funding, collaboration among countries and most cited papers on the renewable energies topic through bibliometric and social network study of articles included in the Web of Science database. 12,167 papers were recovered from 2007 to 2016. Wind power is the energy from which a greater number of articles have been published (n = 3,930), followed by solar energy (n = 2,570) and ocean energy (n = 1,565). The United States leads the world production of articles (n = 2,320), followed by China (n = 1,629), the United Kingdom (n = 1007), Germany (n = 730) and Spain (n = 729). China is the leading country in financed works …