Discovery of Heteroatom‐“Embedded” Te⊂{W<sub>18</sub>O<sub>54</sub>} Nanofunctional Polyoxometalates by Use of Cryospray Mass Spectrometry

Yan, Jun; Long, De‐Liang; Wilson, Elizabeth; Cronin, Leroy

doi:10.1002/anie.200806343

Cited by 90 publications

(50 citation statements)

References 41 publications

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“…As has been described in previous reports, tungstate‐based POM clusters incorporating non‐classical heteroanions are less common because of the stability of their lacunary species . On the other hand, more common mixed valence molybdenum/vanadium‐based POMs templated by non‐traditional heteroanions have been reported .…”

Section: Introductionmentioning

confidence: 83%

“…Alternatively, heteropolyoxometalates, such as the widely investigated Wells–Dawson type [M 18 O 54 (EO 4 ) 2 ] z − clusters, are mainly templated by tetrahedral heteroanions such as phosphates, sulfates or arsenates (E=P, S, As) . In addition there are several examples that incorporate heteroanions in unusual geometries, such as the 18‐molybdopyrophosphate anion, [Mo 18 O 54 (P 2 O 7 )] 4− , templated by a di‐tetrahedral anion with redox inert P V centers, and the [H 3 W 18 O 56 (EO 6 )] 6− anion, which consists of a Dawson‐type {W 18 O 54 } shell enclosing an octahedral (E=Te, I) moiety, which promotes the template‐assisted assembly of the cluster and induces catalytic functionality. Heteropolyoxometalates incorporating one or two templating heteroatoms which adopt non‐tetrahedral geometries are exceedingly rare.…”

Section: Introductionmentioning

confidence: 99%

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Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Sartzi

Long

Sproules

et al. 2018

Chemistry A European J

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Mixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species because they show the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein the incorporation of pyramidal EO heteroanions (E=PH, S, Se, Te) that are responsible not only for directing the templated assembly of a family of mixed-metal POMs but also for the symmetry-breaking of the traditional Dawson architecture and modulation of the electronic characteristics of the cluster's shell. The isolated family of POMs consists of four members: (Me NH ) Na [Mo V O (HPO )]⋅MeOH⋅5 H O (1), (NH ) [Mo V O (SO )]⋅12 H O (2), K [Mo V O (SeO )] ⋅31 H O (3), and (Me NH ) Na[Mo V O (TeO )]⋅15 H O (4), and were characterized by X-ray structural analysis, electrospray ionization mass spectrometry (ESI-MS), thermogravimetric analysis (TGA), UV/Vis, FTIR, elemental analysis, flame atomic absorption spectroscopy (FAAS), and inductively coupled plasma optical emission spectroscopy (ICP-OES). Cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) spectroscopic studies in concert with density functional theoretical (DFT) calculations have been used to elucidate the effect of the heteroatom on the electronic properties of the cluster.

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Section: Introductionmentioning

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Sartzi

Long

Sproules

et al. 2018

Chemistry A European J

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“…The top part is the same as the {W 32 Se 3 } building block mentioned before, and the bottom part contains two {W 9 Se} and four {WO 6 } linkers plus a unique {W 8 Se} fragment. Crucially, the appearance of an additional SeO 3 2À bridging ligand in the {W 7 } unit changes the assembly mode of this fragment, which allows the incorporation of another {WO 6 } to the pentagonal W center, thus the {W 7 } building block found in 1 a and 2 a turns into a {W 8 Se} unit (see Figure 3). This kind of unit is unique since it can be utilized in the construction of high nuclearity clusters and these three clusters are also the first heteropolyoxotungstates isolated that are based on building blocks where molybdate cluster analogues are not known.…”

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confidence: 98%

Development of a Building Block Strategy To Access Gigantic Nanoscale Heteropolyoxotungstates by Using SeO₃²⁻ as a Template Linker

2010

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Polyoxometalates (POMs) have potential in nanoscience due to the range of available building blocks that can allow the assembly of new nano-objects with configurable architectures. [1][2][3][4][5] This, in turn, promises to lead to nanosystems with predefined functions, applications, and the discovery of new phenomena. [6][7][8] Heteropolyoxometalates are an important subset of POMs. Within this class, the choice of the heteroelement not only determines certain physical properties of the cluster, but increasingly has been found to control the range and connectivity of the building blocks. [9][10][11][12] High nuclearity POM clusters based on Mo centers are well known; for example, {Mo 132 } and {Mo 154 } [13][14][15][16] clusters are synthetically accessible due to the occurrence of pentagonal and mixed-valence building blocks. [17][18][19] In contrast, the exploration of high nuclearity polyoxotungstate clusters has yielded different results with somewhat lower nuclearity isopolyoxotungstates: {W 34 } and {W 36 }, [20,21] and has been more limited since tungsten-based building blocks with pentagonal geometries have only very recently been accessed. [22][23] , [25,26] and most recently the synthesis of the spectacular {W 72 Fe 30 } "Keplerate". [23] Herein, we demonstrate that it is possible to generate gigantic heteropolyoxotungstates by utilizing the SeO 3 2À heteroanion. Furthermore, it is possible to control the size, shape, and nuclearity as a function of the ratio of W:Se employed during the synthesis. Structurally, the use of the SeO 3 2À heteroanion effectively prevents the closure of the cluster assemblies to the Keggin-type cluster, and instead gives rise to "open" lacunary {W 9 Se} units, which can be viewed as "inorganic ligands".[ 24À (1 a) shows that the cluster contains three {W 9 Se} subunits with an average SeÀO bond length of 1.72 and a metal core assembled from 16 W centers. The {W 16 } "core" contains a unique {W 7 } building block comprising a pentagonal W{W 4 } unit plus two cornersharing {WO 6 }, as well as a {W 3 O 13 } unit and six {WO 6 } linkers to give a core that has the three {W 9 Se} units bolted on to give the overall cluster. The average WÀO bond length in the pentagonal {WO 7 } unit is 2.01 and it is slightly longer than that found in the {WO 6 } units. Finally, the central {W 3 O 13 } unit (Figure 1) appears to be doubly protonated with the protons located near the central m 3 -O ligand according to the BVS calculations, and the clusters are themselves paired into a 24À (1 a, left) and its building blocks (right): The {SeW 9 } units are shown in cyan, the {W 7 } units are shown in pink, and the pentagonal W center is yellow. The {W 3 O 13 } unit is green and the {WO 6 } and Se linkers are shown in ball-and-stick mode (W: blue, O: pink, Se: green).

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“…Our attempts to prepare this nitrito (ONO) isomer following by the Basolo's procedure [20] 5-(M = Ir and Rh) towards alkali salts NaX (X = NCS -, N 3 -and NO 2 -) was carried out with ESI mass spectrometric techniques. High sensitivity of the method and reliability of data interpretation make ESI-MS a reliable and useful tool in POM chemistry, [23] for example for reaction monitoring [24] or characterization of nanosized POM. [25] (3) A comparison of the reactivity shows several outstanding trends: (i) as previously reported, [14] …”

Section: Introductionmentioning

confidence: 99%

Keggin‐type Polyoxometalates [PW₁₁O₃₉MCl]^5– with Noble Metals (M = Rh and Ir): Novel Synthetic Entries and ESI‐MS Directed Reactivity Screening

Sokolov

Adonin

Sinkevich

et al. 2013

Zeitschrift anorg allge chemie

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Discovery of Heteroatom‐“Embedded” Te⊂{W₁₈O₅₄} Nanofunctional Polyoxometalates by Use of Cryospray Mass Spectrometry

Cited by 90 publications

References 41 publications

Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Development of a Building Block Strategy To Access Gigantic Nanoscale Heteropolyoxotungstates by Using SeO₃²⁻ as a Template Linker

Keggin‐type Polyoxometalates [PW₁₁O₃₉MCl]^5– with Noble Metals (M = Rh and Ir): Novel Synthetic Entries and ESI‐MS Directed Reactivity Screening

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Discovery of Heteroatom‐“Embedded” Te⊂{W18O54} Nanofunctional Polyoxometalates by Use of Cryospray Mass Spectrometry

Cited by 90 publications

References 41 publications

Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Directed Self‐Assembly, Symmetry Breaking, and Electronic Modulation of Metal Oxide Clusters by Pyramidal Heteroanions

Development of a Building Block Strategy To Access Gigantic Nanoscale Heteropolyoxotungstates by Using SeO32− as a Template Linker

Keggin‐type Polyoxometalates [PW11O39MCl]5– with Noble Metals (M = Rh and Ir): Novel Synthetic Entries and ESI‐MS Directed Reactivity Screening

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Discovery of Heteroatom‐“Embedded” Te⊂{W₁₈O₅₄} Nanofunctional Polyoxometalates by Use of Cryospray Mass Spectrometry

Development of a Building Block Strategy To Access Gigantic Nanoscale Heteropolyoxotungstates by Using SeO₃²⁻ as a Template Linker

Keggin‐type Polyoxometalates [PW₁₁O₃₉MCl]^5– with Noble Metals (M = Rh and Ir): Novel Synthetic Entries and ESI‐MS Directed Reactivity Screening