Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution

Kistler ML, Liu T, Gouzerh P, Todea AM, Müller A (2009)
DALTON TRANSACTIONS (26): 5094-5100.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
We report the self-assembly processes in solution of three Keplerate-type molybdenum-oxide based clusters {Mo72V30}, {Mo72Cr30} and {Mo72Fe30} (all with diameters of similar to 2.5 nm). These clusters behave as unique weak polyprotic acids owing to the external water ligands attached to the non-Mo metal centers. Whereas the Cr and Fe clusters have 30 water ligands attached at the 30 M3+ centers pointing outside, {Mo72V30} has 20 water ligands coordinated to vanadium atoms, of which only 10 are pointing outside. The self-assembly processes of the Keplerates leading to supramolecular blackberry-type structures are influenced by the effective charge densities on the cluster surfaces, which can be tuned by the pH values and solvent properties. As expected, {Mo72Cr30} and {Mo72Fe30} behave similarly in aqueous solution due to their analogous structures and in both cases the self-assembly follows the partial deprotonation of the external water ligands attached to the non-Mo metal centers. However, the M-OH2 functionalities differ not only in acidity but also lability, i.e. in different residence times of the H2O ligands. In contrast to {Mo72Cr30} and {Mo72Fe30}, the {Mo72V30} clusters carry a rather large number of negative charges so that their solution properties are different. They exist as discrete macroions in dilute aqueous solution, and form only in mixed water/organic solvent (like acetone) blackberry-type structures whose size increases with acetone content. The comparison of the properties of the clusters allows more general information about the interesting self-assembly phenomenon to be unveiled.
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DALTON TRANSACTIONS
Zeitschriftennummer
26
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5094-5100
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Kistler ML, Liu T, Gouzerh P, Todea AM, Müller A. Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution. DALTON TRANSACTIONS. 2009;(26):5094-5100.
Kistler, M. L., Liu, T., Gouzerh, P., Todea, A. M., & Müller, A. (2009). Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution. DALTON TRANSACTIONS(26), 5094-5100. doi:10.1039/b901505a
Kistler, M. L., Liu, T., Gouzerh, P., Todea, A. M., and Müller, A. (2009). Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution. DALTON TRANSACTIONS, 5094-5100.
Kistler, M.L., et al., 2009. Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution. DALTON TRANSACTIONS, (26), p 5094-5100.
M.L. Kistler, et al., “Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution”, DALTON TRANSACTIONS, 2009, pp. 5094-5100.
Kistler, M.L., Liu, T., Gouzerh, P., Todea, A.M., Müller, A.: Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution. DALTON TRANSACTIONS. 5094-5100 (2009).
Kistler, Melissa L., Liu, Tianbo, Gouzerh, Pierre, Todea, Ana Maria, and Müller, Achim. “Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution”. DALTON TRANSACTIONS 26 (2009): 5094-5100.

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