Hydrogen-bonded assemblies of two-electron reduced mixed-valence [XMo12O40] (X = P and Si) with p-phenylenediamines

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)

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Publisher's URL: http://dx.doi.org/10.1021/ic200683e

Abstract

Hydrogen-bonded assemblies of the two-electron reduced mixed-valence Keggin clusters [PMo12O40](5-) and [SiMo12O40](6-) were obtained by the one-pot electron-transfer reactions between p-phenylenediamine (PPD) or 2,3,5,6-tetramethyl-PPD (TMPPD) (donors) and H+3[PMo12O40](3-) or H+4[SiMo12O40](4-) (acceptors) in CH3CN. The redox states of the [PMo12O40](5-) and [SiMo12O40](6-) clusters were confirmed by the redox titrations and electronic absorption measurements. In (HPPD+)3(H+)2[PMo12O40](5-)(CH3CN)3-6 [1], the N-H ~ O hydrogen-bonded interactions between the monoprotonated HPPD+ (or diprotonated H2PPD2+) and the [PMo12O40](5-) resulted in a windmill-like assembly and hydrophilic one-dimensional channels are formed with a cross-sectional area of 0.065 nm2, and these are filled by the CH3CN molecules. Also, the CH3CN molecules in salt 1 were removed by immersing the single crystals of 1 into H2O, CH3OH, and C2H5OH solvents. In the compound, (HTMPPD+)(6)[SiMo12O40]6-(CH3CN)6 [2], the N-H ~ O hydrogen-bonded interactions between the monoprotonated HTMPPD+ molecules and the [SiMo12O40]6- 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+, while the CH3CN solvent present in salt 2 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
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