3D-2D-0D Stepwise Deconstruction of a Water Framework Templated by a Nanoporous Organic-Inorganic Hybrid Host

authors	Rocha, J; Shi, FN; Paz, FAA; Mafra, L; Sardo, M; Cunha-Silva, L; Chisholm, J; Ribeiro-Claro, P; Trindade, T
nationality	International
journal	CHEMISTRY-A EUROPEAN JOURNAL
author keywords	hybrid materials; hydrogen bonds; ice framework; supramolecular chemistry; water chemistry; X-ray diffraction
keywords	COORDINATION POLYMERS; (H2O)(10) CLUSTER; CRYSTAL; COMPLEX; ACID; TRANSFORMATION; INCLUSION; HEPTAMER; CHAIN
abstract	The supramolecular salt [H(2)pip](3)[Ge(hedp)(2)]center dot 14H(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.
publisher	WILEY-V C H VERLAG GMBH
issn	0947-6539
year published	2010
volume	16
issue	26
beginning page	7741
ending page	7749
digital object identifier (doi)	10.1002/chem.201000431
web of science category	Chemistry, Multidisciplinary
subject category	Chemistry
unique article identifier	WOS:000280431900014