Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action

Korenev VS, Boulay AG, Haouas M, Bannani F, Fedin VP, Sokolov MN, Terazzi E, Garai S, Müller A, Taulelle F, Marrot J, et al. (2014)
Chemistry - A European Journal 20(11): 3097-3105.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Two nanosized polyoxothiometalates were synthesized based on linking oxomolybdate building blocks with {Mo2O2S2}(2+) groups. Remarkably, both compounds are formed selectively primarily upon changing the related concentrations in a logical way; they exhibit common structural features based on the same {Mo9O6S3}-type pores, which result in connections between {Mo6O21} pentagons and {Mo2O2S2}(2+) linkers. Whereas the much larger spherical Mo-132-type Keplerate contains twenty pores, the smaller Mo-63-type cluster remarkably contains only two. The two compounds and a similar Keplerate exhibit interesting supramolecular properties related to interactions with the unusual predominantly apolar NMe4+ cations. Structural characterization of the Mo-63-type compound reveals in the solid state a clathrate-like species that contains four NMe4+ cations embedded in two types of structurally well-adapted pockets. Related NMR spectroscopic investigations in solution using NMe4+ as the NMR spectroscopic probe are in agreement with the solid-state description. (HNMR)-H-1 spectroscopic experiments (1D variable-temperature, 2D total correlation spectroscopy (TOCSY), exchange spectroscopy (EXSY), and diffusion-ordered spectroscopy (DOSY)) feature firmly immobilized and mobile NMe4+ ions in relationship with the type of host-guest arrangements. The use of the (HNMR)-H-1 DOSY spectroscopic methodology has been successfully applied to track the interactions of the NMe4+ cations with the {Mo9O6S3} pores of a sulfurated Keplerate, thereby allowing the first quantitative analysis of this type of plugging process. The stability constant K=(210 +/- 20)mol(-1)L is discussed related to the character of the process.
Stichworte
polyoxometalates; molybdenum; NMR spectroscopy; supramolecular; chemistry; thiometalates
Erscheinungsjahr
2014
Zeitschriftentitel
Chemistry - A European Journal
Band
20
Ausgabe
11
Seite(n)
3097-3105
ISSN
0947-6539
Page URI
https://pub.uni-bielefeld.de/record/2681813

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Korenev VS, Boulay AG, Haouas M, et al. Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action. Chemistry - A European Journal. 2014;20(11):3097-3105.
Korenev, V. S., Boulay, A. G., Haouas, M., Bannani, F., Fedin, V. P., Sokolov, M. N., Terazzi, E., et al. (2014). Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action. Chemistry - A European Journal, 20(11), 3097-3105. doi:10.1002/chem.201303719
Korenev, V. S., Boulay, A. G., Haouas, M., Bannani, F., Fedin, V. P., Sokolov, M. N., Terazzi, E., Garai, S., Müller, A., Taulelle, F., et al. (2014). Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action. Chemistry - A European Journal 20, 3097-3105.
Korenev, V.S., et al., 2014. Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action. Chemistry - A European Journal, 20(11), p 3097-3105.
V.S. Korenev, et al., “Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action”, Chemistry - A European Journal, vol. 20, 2014, pp. 3097-3105.
Korenev, V.S., Boulay, A.G., Haouas, M., Bannani, F., Fedin, V.P., Sokolov, M.N., Terazzi, E., Garai, S., Müller, A., Taulelle, F., Marrot, J., Leclerc, N., Floquet, S., Cadot, E.: Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action. Chemistry - A European Journal. 20, 3097-3105 (2014).
Korenev, Vladimir S., Boulay, Antoine G., Haouas, Mohamed, Bannani, Fatma, Fedin, Vladimir P., Sokolov, Maxim N., Terazzi, Emmanuel, Garai, Somenath, Müller, Achim, Taulelle, Francis, Marrot, Jerome, Leclerc, Nathalie, Floquet, Sebastien, and Cadot, Emmanuel. “Tracking "Apolar" NMe4+ Ions within Two Polyoxothiomolybdates that Have the Same Pores: Smaller Clathrate and Larger Highly Porous Clusters in Action”. Chemistry - A European Journal 20.11 (2014): 3097-3105.

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