Topic
Polyoxometalate
About: Polyoxometalate is a research topic. Over the lifetime, 3493 publications have been published within this topic receiving 94123 citations. The topic is also known as: POM.
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TL;DR: In this paper, the authors showed that three hydroxylated donor molecules derived from tetrathiafulvalene (TTF) or ethylenedithiotetrathyfulvalenes (EDT-TTF), whose crystal structures have been solved by X-ray diffraction, formed complex hydrogen bond networks in the solid state where the oxygen atoms of both the hyroxyl groups and the [Mo6O19]2]-anions act as hydrogen bond acceptors.
Abstract: Electrocrystallization of three hydroxylated donor molecules derived from tetrathiafulvalene (TTF) or ethylenedithiotetrathiafulvalene (EDT-TTF), i.e. Me3TTF-CH2OH, EDT-TTF(CH2OH)2 and TTF(CH2OH)4, in the presence of [n-Bu4N+]2[Mo6O19]2– afforded 2∶1 cation radical salts, [donor+˙]2[Mo6O19]2–, whose crystal structures have been solved by X-ray diffraction. In the three different salts complex hydrogen bond networks develop in the solid state where the oxygen atoms of both the hydroxyl groups and the [Mo6O19]2– anions act as hydrogen bond acceptors. The observed hydrogen bonding directed toward one surface, bridging oxygen atom of [Mo6O19]2– is rationalized by an analysis of ab initio calculations of the distribution of electrostatic potentials.
43 citations
TL;DR: Two polyoxometalate hybrid compounds based on porous metal-organic frameworks (PMOFs/POMs) have been prepared by lithium ion exchange and their crystal structures, stabilities and gas adsorption properties have been characterized.
Abstract: Two polyoxometalate hybrid compounds based on porous metal-organic frameworks (PMOFs/POMs) have been prepared by lithium ion exchange and their crystal structures, stabilities and gas adsorption properties have been characterized. Both compounds consist of neutral Cu 3 (BTC) 2 (BTC = 1,3,5-benzentricarboxylate) metal-organic frameworks (MOFs) as hosts and Keggin polyoxometalates (POMs) anions and lithium ions as guests with the MOFs maintaining their permanent porosity. H 2 adsorption studies demonstrated that the guests play a key role in increasing the H 2 adsorption capacity of the frameworks. With the introduction of POMs and lithium ions, the compounds not only display strong hydrogen adsorption behavior, but also exhibit some differences in H 2 binding energy.
43 citations
TL;DR: It is shown that hybrid 3d metal-containing polyoxometalate systems can be easily built under mild conditions.
Abstract: On the basis of four examples involving various transition-metal cations and various carboxylic acid derivatives, we have shown that hybrid 3d metal-containing polyoxometalate systems can be easily built under mild conditions.
43 citations
TL;DR: In this article, a click chemistry approach was used to synthesize polyoxometalate-polymer hybrids with well-defined structures using a two-azido-containing organosilyl derivative of a Wells-Dawson-type polyoxalate and a propargyl-terminated poly(e-caprolactone).
43 citations
TL;DR: Mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate clusters and gaseous mineral acids.
Abstract: Reactivity descriptors describe catalyst properties that determine the stability of kinetically relevant transition states and adsorbed intermediates. Theoretical descriptors, such as deprotonation energies (DPE), rigorously account for Bronsted acid strength for catalytic solids with known structure. Here, mechanistic interpretations of methanol dehydration turnover rates are used to assess how charge reorganization (covalency) and electrostatic interactions determine DPE and how such interactions are recovered when intermediates and transition states interact with the conjugate anion in W and Mo polyoxometalate (POM) clusters and gaseous mineral acids. Turnover rates are lower and kinetically relevant species are less stable on Mo than W POM clusters with similar acid strength, and such species are more stable on mineral acids than that predicted from W-POM DPE–reactivity trends, indicating that DPE and acid strength are essential but incomplete reactivity descriptors. Born–Haber thermochemical cycles i...
43 citations