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: A new approach to prepare heterometallic cluster organic frameworks has been developed that facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework.
Abstract: A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework.
141 citations
TL;DR: The effect of cation size on the rate and energy of electron transfer to [(M(+))(acceptor)] ion pairs is addressed by assigning key physicochemical properties (reactivity, relative energy, structure, and size) to an isoelectronic series of well-defined M(+)-acceptor pairs.
Abstract: The effect of cation size on the rate and energy of electron transfer to [(M+)(acceptor)] ion pairs is addressed by assigning key physicochemical properties (reactivity, relative energy, structure, and size) to an isoelectronic series of well-defined M+−acceptor pairs, M+ = Li+, Na+, K+. A 1e- acceptor anion, α-SiVVW11O405- (1, a polyoxometalate of the Keggin structural class), was used in the 2e- oxidation of an organic electron donor, 3,3‘,5,5‘-tetra-tert-butylbiphenyl-4,4‘-diol (BPH2), to 3,3‘,5,5‘-tetra-tert-butyldiphenoquinone (DPQ) in acetate-buffered 2:3 (v/v) H2O/t-BuOH at 60 °C (2 equiv of 1 are reduced by 1e- each to 1red, α-SiVIVW11O406-). Before an attempt was made to address the role of cation size, the mechanism and conditions necessary for kinetically well behaved electron transfer from BPH2 to 1 were rigorously established by using GC−MS, 1H, 7Li, and 51V NMR, and UV−vis spectroscopy. At constant [Li+] and [H+], the reaction rate is first order in [BPH2] and in [1] and zeroth order in [1re...
141 citations
TL;DR: The ruthenium-substituted "sandwich" type polyoxometalate [WZnRuIII2(XW9O34)2]11- where X = ZnII or CoII has been shown to be unique in its ability to be selective hydroxylation of adaman as discussed by the authors.
Abstract: The ruthenium-substituted “sandwich” type polyoxometalate [WZnRuIII2(XW9O34)2]11- where X = ZnII or CoII has been shown to be unique in its ability to catalyze the selective hydroxylation of adaman...
138 citations
TL;DR: The previously unknown titanium(IV)-containing mu-hydroxo dimeric heteropolytungstate (Bu4N)7[(PTiW11O39)2-OH] (TBA salt of H1) has been synthesized and shows higher catalytic activity than 2 for thioether oxidation by hydrogen peroxide in acetonitrile.
Abstract: The previously unknown titanium(IV)-containing μ-hydroxo dimeric heteropolytungstate (Bu4N)7[(PTiW11O39)2OH] (TBA salt of H1) has been synthesized, starting from H5PTiW11O40, and characterized by elemental analysis, multinuclear (31P, 17O, 183W) NMR, IR, FAB-MS, cyclic voltammetry, and potentiometric titration. 31P NMR reveals that H1 (δ −12.76) readily forms in MeCN from the Keggin monomer (POM), PTiW11O405- (2, δ −13.34), upon the addition of 1.5 equiv of H+, via the protonated species, P(TiOH)W11O394- (H2, δ −13.44). The ratio of H1, 2, and H2, which are present in equilibrium in MeCN solution at 25 °C, depends on the concentration of both H+ and H2O. The Ti−O−Ti linkage readily reacts with nucleophilic reagents, such as H2O and ROH, to yield monomeric Keggin derivatives. μ-Hydroxo dimer H1 shows higher catalytic activity than 2 for thioether oxidation by hydrogen peroxide in acetonitrile. The reaction proceeds readily at room temperature and affords the corresponding sulfoxide and sulfone in ca. quant...
138 citations
TL;DR: The autoassembly process of copper-oxalate dimers and Keggin type polyoxometalates leads to the first example of a new family of organic-inorganic hybrids, K(14), which reveals the presence of a polymeric hybrid built up of alternating dimer and polyoxometricalate entities.
Abstract: The autoassembly process of copper-oxalate dimers and Keggin type polyoxometalates leads to the first example of a new family of organic-inorganic hybrids, K(14)[(Cu(2)(bpy)(2)(mu-ox))(SiW(11)O(39)Cu(H(2)O))](2)[SiW(11)O(39)Cu(H(2)O)]. approximately 55H(2)O. This compound crystallizes in the monoclinic space group C2/m, a = 37.932(6) A, b = 21.303(3) A, c = 12.546(2) A, beta = 106.16(1) degrees, Z = 2. The crystal structure reveals the presence of a polymeric hybrid built up of alternating dimer and polyoxometalate entities.
137 citations