Premium
3D–2D–0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic–Inorganic Hybrid Host
Author(s) -
Rocha João,
Shi FaNian,
Paz Filipe A. Almeida,
Mafra Luís,
Sardo Mariana,
CunhaSilva Luís,
Chisholm James,
RibeiroClaro Paulo,
Trindade Tito
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000431
Subject(s) - nanoporous , thermogravimetric analysis , supramolecular chemistry , molecule , hybrid material , deprotonation , crystallography , materials science , infrared spectroscopy , raman spectroscopy , spectroscopy , metal organic framework , mesoporous material , salt (chemistry) , chemistry , inorganic chemistry , crystal structure , nanotechnology , organic chemistry , ion , adsorption , catalysis , physics , quantum mechanics , optics
Abstract The supramolecular salt [H 2 pip] 3 [Ge(hedp) 2 ]⋅14 H 2 O ( 1 ) [H 2 pip 2+ =piperazine cation C 4 H 12 N 2 2+ ; hedp 5− =deprotonated form of etidronic acid, C 2 H 3 P 2 O 7 5− ) is reported. This consists of an organic–inorganic hybrid hydrogen‐bonded nanoporous framework, the internal surface of which acts as a template for the three‐dimensional (3D) clustering of water molecules. The structure and molecular dynamics of this material are characterised by single‐crystal X‐ray diffraction, thermogravimetric analysis, Raman (H/D isotopic substitution) spectroscopy, and 2 H solid‐state (wide‐line and MAS) NMR spectroscopy. Material 1 is shown to be unusual because 1) few nanoporous materials exhibit a well‐organised 3D framework of water molecules, 2) it provides a unique opportunity to follow experimentally and to rationalise the deconstruction of a 3D water framework and 3) despite the fact that the hybrid framework is a supramolecular salt, the structure does not collapse after dehydration and the final material is crystalline.