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.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ; ; ; ; ; ; ; ; ;
All
Abstract
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.
Publishing Year
ISSN
PUB-ID

Cite this

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.
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.
This data publication is cited in the following publications:
This publication cites the following data publications:

86 References

Data provided by Europe PubMed Central.


AUTHOR UNKNOWN, Angew. Chem. Int. Ed. 48(), 2009
Predicting a structured future.
Muller A., Nat Chem 1(1), 2009
PMID: 21378785
A further step towards tuning the properties of metal-chalcogenide nanocapsules by replacing skeletal oxide by sulphide ligands.
Schaffer C, Todea AM, Bogge H, Floquet S, Cadot E, Korenev VS, Fedin VP, Gouzerh P, Muller A., Dalton Trans 42(2), 2013
PMID: 23147405

Merca, Chem. Commun. (), 2008

AUTHOR UNKNOWN, 0

García-Tarrés, J. Phys. Chem. B 102(), 1998

Jorgensen, J. Phys. Chem. 90(), 1986

AUTHOR UNKNOWN, 0

Turner, J. Chem. Phys. 102(), 1995

Grego, Angew. Chem. 125(), 2013

AUTHOR UNKNOWN, Angew. Chem. Int. Ed. 52(), 2013

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 24519761
PubMed | Europe PMC

Search this title in

Google Scholar