Akutagawa, T., Kudo, F., Tsunashima, R., Noro, S., Cronin, L. and Nakamura, T. (2011) Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines. Inorganic Chemistry, 50(14), pp. 6711-6718. (doi: 10.1021/ic200683e)
Full text not currently available from Enlighten.
Publisher's URL: http://dx.doi.org/10.1021/ic200683e
Abstract
Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo<sub>12</sub>O<sub>40</sub>](<sup>5-</sup>) and [SiMo<sub>12</sub>O<sub>40</sub>](<sup>6-</sup>) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H<sup>+</sup><sub>3</sub>[PMo<sub>12</sub>O<sub>40</sub>](<sup>3-</sup>) or H<sup>+</sup><sub>4</sub>[SiMo<sub>12</sub>O<sub>40</sub>](<sup>4-</sup>) (acceptors) in CH<sub>3</sub>CN. The redox states of the [PMo<sub>12</sub>O<sub>40</sub>](<sup>5-</sup>) and [SiMo<sub>12</sub>O<sub>40</sub>](<sup>6-</sup>) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD<sup>+</sup>)<sub>3</sub>(H<sup>+</sup>)<sub>2</sub>[PMo<sub>12</sub>O<sub>40</sub>](<sup>5-</sup>)(CH<sub>3</sub>CN)<sub>3-6</sub> [<b>1</b>], the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD<sup>+</sup> (or diprotonated H2PPD<sup>2+</sup>) and the [PMo<sub>12</sub>O<sub>40</sub>](<sup>5-</sup>) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm<sup>2</sup>, and these are filled by the CH<sub>3</sub>CN molecules. Also, the CH<sub>3</sub>CN molecules in salt <b>1</b> were removed by immersing the single crystals of <b>1</b> into H<sub>2</sub>O, CH<sub>3</sub>OH, and C<sub>2</sub>H<sub>5</sub>OH solvents. In the compound, (HTMPPD<sup>+</sup>)(<sub>6</sub>)[SiMo<sub>12</sub>O<sub>40</sub>]<sup>6-</sup>(CH<sub>3</sub>CN)<sup>6</sup> [<b>2</b>], the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD<sup>+</sup> molecules and the [SiMo<sub>12</sub>O<sub>40</sub>]<sup>6-</sup> formed a "Saturn-ring"-like assembly. Each Saturn-ring was arranged into an hexagonally packed array via hydrogen-bonded and Π-stacking interactions of HTMPPD<sup>+</sup>, while the CH<sub>3</sub>CN solvent present in salt <b>2</b> are only found in the zero-dimensional isolated cavities.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Cronin, Professor Lee |
| Authors: | Akutagawa, T., Kudo, F., Tsunashima, R., Noro, S., Cronin, L., and Nakamura, T. |
| Subjects: | Q Science > QD Chemistry |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Inorganic Chemistry |
| ISSN: | 0020-1669 |
| Related URLs: |
University Staff: Request a correction | Enlighten Editors: Update this record
Altmetric
Altmetric