Journal article
Gated and Differently Functionalized (New) Porous Capsules Direct Encapsulates' Structures: Higher and Lower Density Water
Chemistry : a European journal, Vol.15(8), pp.1844-1852
02/09/2009
DOI: 10.1002/chem.200801602
PMID: 19130528
Abstract
By the deliberate choice of the internal ligands of the porous nanocapsules [{Mo)Mo-5}(12){Mo-2-(ligand)}(30)](n-), the respective cavities' shells can be differently sized/functionalized. This allows one to trap the same large number of water molecules, that is, 100 in a capsule cavity with formate ligands having a larger space available, as well as in a cavity containing sulfates and hypophosphites, that is, with less space. Whereas the 100 molecules fill the space completely in the second case in which they are organized in three shells, a four-shell system with underoccupation and broken hydrogen bonds is observed in the other case. This is an unprecedented result in terms of the structurally well defined special forms of "higher and lower density" water molecule assemblies. Precisely, by replacing the larger ligands in the mentioned nanocapsule type by formates, voids in the capsule cavity of (HC(NH2)(2))(22)[{(HC(NH2)(2))(20) + (H2O)(100)}subset of{(Mo)Mo5O21(H2O)(6)}(12)- {Mo2O4(HCO2)}(30)]center dot ca.200H(2)O are generated that get filled with water molecules concomitant with an expansion of the three to four shell {H2O}(100) cluster. The water shells in both capsules containing different ligands are organized in the form of dodecahedra (partly with underoccupation) and a strongly distorted rhombicosidodecahedron spanned by a {H2O}(60)={(H2O)(5)}(12) aggregate. The well-defined water shells only emerge if cations cannot enter into the capsules, which is achieved by closing the pores with plugs/guests such as formamidinium cations. The work is based on the syntheses of two new compounds, related single-crystal X-ray diffraction studies, and molecular dynamics simulations, which show remarkably that water molecule shell structuring occurs in the capsules due to the confined conditions even in the case of open pores and at room temperature if cation uptake is prevented.
Details
- Title: Subtitle
- Gated and Differently Functionalized (New) Porous Capsules Direct Encapsulates' Structures: Higher and Lower Density Water
- Creators
- Tamoghna Mitra - Bielefeld UniversityPere Miro - Institut Català d'Investigació QuímicaAdrian-Raul Tomsa - Univ Bielefeld, Fak Chem, D-33501 Bielefeld, GermanyAlice Merca - Bielefeld UniversityHartmut Boegge - Univ Bielefeld, Fak Chem, D-33501 Bielefeld, GermanyJosep Bonet Avalos - Universidad Rovira i VirgiliJosep Maria Poblet - Universidad Rovira i VirgiliCarles Bo - Universidad Rovira i VirgiliAchim Mueller - Univ Bielefeld, Fak Chem, D-33501 Bielefeld, Germany
- Resource Type
- Journal article
- Publication Details
- Chemistry : a European journal, Vol.15(8), pp.1844-1852
- Publisher
- Wiley
- DOI
- 10.1002/chem.200801602
- PMID
- 19130528
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- Number of pages
- 9
- Grant note
- European Union; European Union (EU) CTQ2005-0609-CO2-02/BQU; CTQ2004-03346/ PPQ / MEC of the Government of Spain Volkswagenstiftung; Volkswagen ICIQ Foundation; Foundation CELLEX German-Israeli Foundation for Scientific Research Development; German-Israeli Foundation for Scientific Research and Development 2007FIC00043 / Generalitat de Catalunya for a FI fellowship; Generalitat de Catalunya 2010 CSD2006-0003 / Consolider Ingenio; Spanish Government Fonds der Chernischen Industric SGR01-00315; 2005SGR00715; 2005SGR00104 / CIRIT of the Catalan Government Deutsche Forschungsgemeinschaft (together with the National Science Foundation (USA)),; German Research Foundation (DFG)
- Language
- English
- Date published
- 02/09/2009
- Academic Unit
- Chemistry
- Record Identifier
- 9984618638402771
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