RT Journal Article
T1 Multifunctional Luminescent and Proton-Conducting Lanthanide Carboxyphosphonate Open-Framework Hybrids Exhibiting Crystalline-to-Amorphous-to-Crystalline Transformations
A1 Pérez-Colodrero, Rosario Mercedes
A1 Papathanasiou, Konstantinos E.
A1 Stavgianoudaki, Nikoleta
A1 Olivera-Pastor, Pascual
A1 Losilla, Enrique R.
A1 García-Aranda, Miguel Ángel
A1 León-Reina, Laura
A1 Sanz, Jesús
A1 Sobrados, Isabel
A1 Choquesillo-Lazarte, Duane
A1 García-Ruíz, Juan M.
A1 Atienzar, Pedro
A1 Rey, Fernando
A1 Demadis, Konstantinos D.
A1 Cabeza-Díaz, Aurelio
K1 Cristalografía
K1 Materiales
K1 Química
AB The chemistry of metal phosphonates has been progressing fast with the addition of new materials that possess novel structural features and new properties, occasionally in a cooperative manner. In this paper, we report a new family of functional lanthanide-carboxyphosphonate materials. Specifically, the lanthanide is La, Ce, Pr, Sm, Eu, Gd, Tb, or Dy and the carboxyphosphonate ligand is 2-hydroxyphosphonoacetic acid (H3HPA) . All reported LnHPA compounds, Ln3(H0.75O3PCHOHCOO)4·xH2O (x = 15−16), crystallize in the orthorhombic system. Two types of structures were isolated: series I and II polymorphs. For both series, the three-dimensional (3D) open frameworks result from the linkage of similar organo-inorganic layers, in the ac-plane, by central lanthanide cations, which yield trimeric units also found in other metal-HPA hybrids. Large oval-shaped 1D channels are formed by the spatial separation of the layers along the b-axis and filled with lattice water molecules. LnHPA materials undergo remarkable crystalline-to-amorphous-to crystalline transformations upon dehydration and rehydration cycles, as confirmed by thermodiffraction and NMR spectroscopy. The highest proton conductivity was observed for GdHPA (series II), 3.2 × 10−4 S cm−1 at 98% RH and T = 21 °C. The dehydration−rehydration chemistry was also followed by photoluminescence spectroscopy. It was shown that loss and reuptake of water molecules are accompanied by clear changes in the photoluminescence spectra and lifetimes of the Eu analog (series II). Our present results reveal a wide family of wellcharacterized, multifunctional lanthanide based phosphonate 3D-structured metal−organic frameworks (MOFs) that show reversible crystalline-to-amorphous-to-crystalline transformations and, at the same time, exhibit high proton conductivity.
PB American Chemical Society
YR 2012
FD 2012-09-15
LK https://hdl.handle.net/10630/21037
UL https://hdl.handle.net/10630/21037
LA eng
NO Chem. Mater. 2012, 24, 3780−3792
NO Proyecto nacional MAT2010-15175
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 4 mar 2026