title: 3D-2D-0D stepwise deconstruction of a water framework templated by a nanoporous organic-inorganic hybrid host.
abstract: The supramolecular salt [H(2)pip](3)[Ge(hedp)(2)].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.
authors.affiliation: Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. rocha@ua.pt
authors.forename: João
authors.initials: J
authors.lastname: Rocha
authors.forename: Fa-Nian
authors.initials: FN
authors.lastname: Shi
authors.forename: Filipe A Almeida
authors.initials: FA
authors.lastname: Paz
authors.forename: Luís
authors.initials: L
authors.lastname: Mafra
authors.forename: Mariana
authors.initials: M
authors.lastname: Sardo
authors.forename: Luís
authors.initials: L
authors.lastname: Cunha-Silva
authors.forename: James
authors.initials: J
authors.lastname: Chisholm
authors.forename: Paulo
authors.initials: P
authors.lastname: Ribeiro-Claro
authors.forename: Tito
authors.initials: T
authors.lastname: Trindade
mesh_terms: D002412:Cations / Q000737:chemistry; D002678:Chimera; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010879:Piperazines / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D002412:Cations; D010879:Piperazines; D014867:Water