abstract
A series of two-dimensional lanthanide-organic materials (LnOFs), [Ln(H(3)NMP)]center dot 1.5H(2)O [Ln(3+) = La(3+) (1), Pr(3+) (2), Nd(3+) (3), Sm(3+) (4), or Eu(3+) (5); H(3)NMP(3-) is a residue of nitrilotris(methylenephosphonic acid)], has been isolated as microcrystalline powders from hydrothermal synthesis and characterized by high-resolution laboratory and synchrotron powder X-ray diffraction (PXRD), solid-state NMR, FTIR and FT Raman spectroscopies, CHN elemental analysis, thermogravimetry, scanning electron microscopy, and energy dispersive analysis of X-ray spectroscopy. The crystal structure of [Pr(H(3)NMP)]center dot 1.5H(2)O (2) has been solved from a combined study of ab initio methods using high-resolution PXRD data and high-resolution solid-state NMR techniques performed on [La(H(3)NMP)]center dot 1.5H(2)O (1) ((13)C, (15)N, (31)P CPMAS and 2D (1)H-(1)H/(31)P HOMCOR/HETCOR). The structure contains a single lanthanide center which does not have water molecules in its first coordination sphere. This Ln(3+) center acts as the node of a neutral undulated two-dimensional network, (2)(infinity)[Pr(H(3)NMP)], having a (4,4) topology, which close packs along the [100] direction of the unit cell (adjacent layers are related by inversion). Water molecules of crystallization occupy the interlayer spaces, and a one-dimensional water cluster (spiral chain topology) is confined to the channels formed by the packing of adjacent layers. Removal of these water molecules (investigated by variable-temperature PXRD) leads to a new crystalline phase with a smaller interlayer space. The material partially reabsorbs water from the surrounding environment, originating the parent phase. This dehydration/rehydration process has also been monitored by photoluminescence (PL) spectroscopy, revealing that the presence of water in the interlayer spaces does not affect much the PL properties of [Eu(H(3)NMP)]center dot 1.5H(2)O (5).
keywords
DIMENSIONAL COORDINATION POLYMER; METAL-PHOSPHONATE CHEMISTRY; STRUCTURAL-CHARACTERIZATION; HYDROTHERMAL SYNTHESIS; CRYSTAL-STRUCTURES; FRAMEWORK STRUCTURE; MAGNETIC-BEHAVIOR; DICHOTOMY METHOD; RATIONAL DESIGN; TRIMESIC ACID
subject category
Chemistry; Materials Science
authors
Cunha-Silva, L; Mafra, L; Ananias, D; Carlos, LD; Rocha, J; Paz, FAA
our authors
Duarte Ananias
Assistant Researcher
Filipe Alexandre Almeida Paz
Principal Researcher
João Rocha
Full Professor
Luís Carlos
Full professor