Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell

Todea AM, Szakacs J, Konar S, Bögge H, Crans DC, Glaser T, Rousseliere H, Thouvenot R, Gouzerh P, Müller A (2011)
Chemistry 17(24): 6635-6642.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Autor
; ; ; ; ; ; ; ; ;
Abstract / Bemerkung
The present study refers to a variety of reduced metal-oxide core-shell hybrids, which are unique with regard to their electronic structure, their geometry, and their formation. They contain spherical {Mo(72)Fe(30)} Keplerate-type shells encapsulating Keggin-type polyoxomolybdates based on very weak interactions. Studies on the encapsulation of molybdosilicate as well as on the earlier reported molybdophosphate, coupled with the use of several physical methods for the characterization led to unprecedented results (see title). Upon standing in air at room temperature, acidified aqueous solutions obtained by dissolving sodium molybdate, iron(II) chloride, acetic acid, and molybdosilicic acid led to the precipitation of monoclinic greenish crystals (1). A rhombohedral variant (2) has also been observed. Upon drying at room temperature, compound 3 with a layer structure was obtained from 1 in a solid-state reaction based on cross-linking of the shells. The compounds 1, 2, and 3 have been characterized by a combination of methods including single-crystal X-ray crystallography, magnetic studies, as well as IR, Mossbauer, (resonance) Raman, and electronic absorption spectroscopy. In connection with detailed studies of the guest-free two-electron-reduced {Mo(72)Fe(30)}-type Keplerate (4) and of the previously reported molybdophosphate-based hybrids (including (31)P NMR spectroscopy results), it is unambiguously proved that 1, 2, and 3 contain non-reduced Keggin ion cores and reduced {Mo(72)Fe(30)}-type shells. The results are discussed in terms of redox considerations (the shell as well as the core can be reduced) including those related to the reduction of "molybdates" by Fe(II) being of interdisciplinary including catalytic interest (the Mo(VI)/Mo(V) and Fe(III)/Fe(II) couples have very close redox potentials!), while also referring to the special formation of the hybrids based on chemical Darwinism.
Erscheinungsjahr
Zeitschriftentitel
Chemistry
Band
17
Zeitschriftennummer
24
Seite
6635-6642
ISSN
PUB-ID

Zitieren

Todea AM, Szakacs J, Konar S, et al. Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell. Chemistry. 2011;17(24):6635-6642.
Todea, A. M., Szakacs, J., Konar, S., Bögge, H., Crans, D. C., Glaser, T., Rousseliere, H., et al. (2011). Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell. Chemistry, 17(24), 6635-6642. doi:10.1002/chem.201003260
Todea, A. M., Szakacs, J., Konar, S., Bögge, H., Crans, D. C., Glaser, T., Rousseliere, H., Thouvenot, R., Gouzerh, P., and Müller, A. (2011). Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell. Chemistry 17, 6635-6642.
Todea, A.M., et al., 2011. Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell. Chemistry, 17(24), p 6635-6642.
A.M. Todea, et al., “Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell”, Chemistry, vol. 17, 2011, pp. 6635-6642.
Todea, A.M., Szakacs, J., Konar, S., Bögge, H., Crans, D.C., Glaser, T., Rousseliere, H., Thouvenot, R., Gouzerh, P., Müller, A.: Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell. Chemistry. 17, 6635-6642 (2011).
Todea, Ana Maria, Szakacs, Julia, Konar, Sanjit, Bögge, Hartmut, Crans, Debbie C., Glaser, Thorsten, Rousseliere, Helene, Thouvenot, Rene, Gouzerh, Pierre, and Müller, Achim. “Reduced Molybenum-Oxide-Based Core-Shell Hybrids: "Blue" Electrons Are Delocalized on the Shell”. Chemistry 17.24 (2011): 6635-6642.

3 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12Fe(III)30 (M = Mo(VI), W(VI)).
Kuepper K, Derks C, Taubitz C, Prinz M, Joly L, Kappler JP, Postnikov A, Yang W, Kuznetsova TV, Wiedwald U, Ziemann P, Neumann M., Dalton Trans 42(22), 2013
PMID: 23403844

83 References

Daten bereitgestellt von Europe PubMed Central.


AUTHOR UNKNOWN, 0

Müller, Chem. Commun. (), 1999

Kögerler, 2003
Unveiling the transient template in the self-assembly of a molecular oxide nanowheel.
Miras HN, Cooper GJ, Long DL, Bogge H, Muller A, Streb C, Cronin L., Science 327(5961), 2010
PMID: 20044572

Borrás-Almenar, Chem. Phys. 195(), 1995

Borrás-Almenar, Chem. Phys. 195(), 1995

AUTHOR UNKNOWN, 0

Cronin, 2004

Gouzerh, L’Actualité Chimique 298(), 2006

AUTHOR UNKNOWN, 0

Mitchell, Nature 348(), 1990

Emsley, New Scienstist 1744(), 1990

Pope, Nature 355(), 1992
Calcium control and InsP4.
Irvine RF., Nature 352(6331), 1991
PMID: 2067573

Reuter, Angew. Chem. 104(), 1992

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. Engl. 31(), 1992

Baxter, 1996

Gross, Chem. Br. 8(), 2003

Müller, Angew. Chem. 107(), 1995

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. Engl. 34(), 1995

Müller, Angew. Chem. 112(), 2000

Uppenbrink, Science 290(), 2000

Müller, Chem. Commun. (), 2001

Müller, Angew. Chem. 111(), 1999
Archimedean Synthesis and Magic Numbers: "Sizing" Giant Molybdenum-Oxide-Based Molecular Spheres of the Keplerate Type.
Muller A, Sarkar S, Shah SQ, Bogge H, Schmidtmann M, Kogerler P, Hauptfleisch B, Trautwein AX, Schunemann V V., Angew. Chem. Int. Ed. Engl. 38(21), 1999
PMID: 10556914

Müller, Angew. Chem. 112(), 2000

Müller, Solid State Sci. 2(), 2000

AUTHOR UNKNOWN, 0
Soluble molybdenum blues-"des Pudels Kern".
Muller A, Serain C., Acc. Chem. Res. 33(1), 2000
PMID: 10639070

Müller, Angew. Chem. 114(), 2002

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. 41(), 2002

Botar, Angew. Chem. 121(), 2009
Electronic control of spin coupling in keplerate-type polyoxomolybdates.
Botar B, Ellern A, Hermann R, Kogerler P., Angew. Chem. Int. Ed. Engl. 48(48), 2009
PMID: 19859930

AUTHOR UNKNOWN, 0

Pope, 1983

Pope, 2003

Pope, Angew. Chem. 103(), 1991

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. Engl. 30(), 1991

AUTHOR UNKNOWN, 0

Massart, Ann. Chim. 3(), 1968

Massart, Ann. Chim. 4(), 1969

Fruchart, C. R. Acad. Sc. Paris Série C 266(), 1968

AUTHOR UNKNOWN, 0

Langpape, Appl. Catal. A 200(), 2000

Borshch, Appl. Catal. A 200(), 2000
Iron-Molybdenum Electron Delocalization in Substituted Keggin Polyoxoanions.
Duclusaud H, Borshch SA., Inorg Chem 38(15), 1999
PMID: 11671094

Min, Catal. Today 66(), 2001

Schäffer, Angew. Chem. 121(), 2009
Unprecedented and differently applicable pentagonal units in a dynamic library: a keplerate of the type {(W)W5}12{Mo2}30.
Schaffer C, Merca A, Bogge H, Todea AM, Kistler ML, Liu T, Thouvenot R, Gouzerh P, Muller A., Angew. Chem. Int. Ed. Engl. 48(1), 2009
PMID: 19035609
Self-recognition among different polyprotic macroions during assembly processes in dilute solution.
Liu T, Langston ML, Li D, Pigga JM, Pichon C, Todea AM, Muller A., Science 331(6024), 2011
PMID: 21436449

AUTHOR UNKNOWN, 0

Müller, Coord. Chem. Rev. 222(), 2001

Müller, Nature 447(), 2007

Todea, Angew. Chem. 122(), 2010
Porous capsules {(M)M(5)}(12)Fe(III) (30) (M=Mo(VI), W(VI)): sphere surface supramolecular chemistry with 20 ammonium ions, related solution properties, and tuning of magnetic exchange interactions.
Todea AM, Merca A, Bogge H, Glaser T, Pigga JM, Langston ML, Liu T, Prozorov R, Luban M, Schroder C, Casey WH, Muller A., Angew. Chem. Int. Ed. Engl. 49(3), 2010
PMID: 20013836

AUTHOR UNKNOWN, 0

Rocchiccioli-Deltcheff, Spectrochim. Acta, Part A 32(), 1976

AUTHOR UNKNOWN, 0

Müller, J. Chem. Phys. 61(), 1974
A study of the formation, purification and application as a SWNT growth catalyst of the nanocluster [HxPMo12O40[subset]H4Mo72Fe30(O2CMe)15O254(H2O)98].
Anderson RE, Colorado R Jr, Crouse C, Ogrin D, Maruyama B, Pender MJ, Edwards CL, Whitsitt E, Moore VC, Koveal D, Lupu C, Stewart MP, Smalley RE, Tour JM, Barron AR., Dalton Trans (25), 2006
PMID: 16786068

Ogrin, J. Cluster Sci. 18(), 2007
Classical and quantum magnetism in giant Keplerate magnetic molecules.
Muller A, Luban M, Schroder C, Modler R, Kogerler P, Axenovich M, Schnack J, Canfield P, Bud'ko S, Harrison N., Chemphyschem 2(8-9), 2001
PMID: 23686989
Ferrimagnetically ordered nanosized polyoxomolybdate-based cluster spheres.
Botar B, Kogerler P, Muller A, Garcia-Serres R, Hill CL., Chem. Commun. (Camb.) (45), 2005
PMID: 16292368

Müller, Angew. Chem. 112(), 2000
Thirty Electrons "Trapped" in a Spherical Matrix: A Molybdenum Oxide-Based Nanostructured Keplerate Reduced by 36 Electrons.
Muller A, Shah SQ, Bogge H, Schmidtmann M, Kogerler P, Hauptfleisch B, Leiding S, Wittler K., Angew. Chem. Int. Ed. Engl. 39(9), 2000
PMID: 10820451

Sanchez, J. Am. Chem. Soc. 104(), 1982

Barrows, 1990

Artero, Eur. J. Inorg. Chem. (), 2000

AUTHOR UNKNOWN, 0
Proton-coupled electron transfer.
Cukier RI, Nocera DG., Annu Rev Phys Chem 49(), 1998
PMID: 9933908
Proton-coupled electron transfer: a reaction chemist's view.
Mayer JM., Annu Rev Phys Chem 55(), 2004
PMID: 15117257

Meyer, Angew. Chem. 119(), 2007
The possible role of proton-coupled electron transfer (PCET) in water oxidation by photosystem II.
Meyer TJ, Huynh MH, Thorp HH., Angew. Chem. Int. Ed. Engl. 46(28), 2007
PMID: 17604381
Proton-coupled electron transfer.
Huynh MH, Meyer TJ., Chem. Rev. 107(11), 2007
PMID: 17999556
Concerted proton-electron transfers: electrochemical and related approaches.
Costentin C, Robert M, Saveant JM., Acc. Chem. Res. 43(7), 2010
PMID: 20232879
Reduction of O2 to superoxide anion (O2.-) in water by heteropolytungstate cluster-anions.
Geletii YV, Hill CL, Atalla RH, Weinstock IA., J. Am. Chem. Soc. 128(51), 2006
PMID: 17177455
Concerted proton-electron transfer to dioxygen in water.
Snir O, Wang Y, Tuckerman ME, Geletii YV, Weinstock IA., J. Am. Chem. Soc. 132(33), 2010
PMID: 20684537

AUTHOR UNKNOWN, 0

Neumann, J. Am. Chem. Soc. 114(), 1992

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 21542032
PubMed | Europe PMC

Suchen in

Google Scholar