3D-2D-0D stepwise deconstruction of a water framework templated by a nanoporous organic-inorganic hybrid host.
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.
Rocha
João
J
Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. rocha@ua.pt
Shi
Fa-Nian
FN
Paz
Filipe A Almeida
FA
Mafra
Luís
L
Sardo
Mariana
M
Cunha-Silva
Luís
L
Chisholm
James
J
Ribeiro-Claro
Paulo
P
Trindade
Tito
T
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*
D002412:Cations; D010879:Piperazines; D014867:Water