Modelling the Luminescence of Phosphonate Lanthanide–Organic Frameworks. Issue 7 (4th September 2014)

• Record Type: Journal Article
• Authors: Nolasco, Mariela M.; Mendes, Ricardo F.; Lima, Patrícia P.; Almeida Paz, Filipe A.; Carlos, Luís D.; Rocha, João
• Other Names: Leroux Fabrice sponsoringEditor.; Rabu Pierre sponsoringEditor.; Sommerdijk Nico A. J. M. sponsoringEditor.; Taubert Andreas sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 7(2015)
• Page Start: 1254
• Page End: 1260
• Publication Date: 2014-09-04
• Subjects: Metal–organic frameworks -- Energy transfer -- Luminescence -- Lanthanides -- Phosphonate ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402492
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The suitability of the computer package LUMPAC to calculate the photoluminescence properties of metal–organic frameworks was assessed by considering three systems based on the ditopic 1, 4‐phenylenebis(methylene)diphosphonic acid (H4 pmd) ligand and Ln 3+ ions, namely, [Eu(Hpmd)(H2 O)] (1 ), [La2 (H2 pmd)(pmd)(H2 O)2 ] (2 ) and [La2 (H2 pmd)3 (H2 O)12 ] (3, previously reported) and their isotypical materials doped with Eu 3+ cations, [(La0.95 Eu0.05 )2 (H2 pmd)(pmd)(H2 O)2 ] (4 ) and [(La0.95 Eu0.05 )2 (H2 pmd)3 (H2 O)12 ] (5 ). These materials were prepared, and their structures and luminescence properties were characterized. A straightforward approximation based on the simple crystallographic structural subunits of these materials was used and resulted in an excellent agreement between the calculated and experimental properties. The intramolecular energy transfer and back‐transfer rates were predicted, and the T1 → 5 D1 channel was shown to be the dominant pathway (9.03 × 10 4 s –1 for1, 1.06 × 10 4 s –1 for4 and 2.18 × 10 5 s –1 for5 ). Abstract : The applicability of the LUMPAC software for calculations of the photoluminescence properties of metal–organic frameworks is assessed by considering three systems with a ditopic 1, 4‐phenylenebis(methylene)diphosphonic acid ligand and Eu 3+ ions. A simple method based on the crystallographic structural subunits affords excellent agreement between the calculated and experimental photoluminescence.