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Relationships Between Structure and Spectroscopic Properties of Nd 3+ Ethylenediaminetetramethylenephosphonates and Ethylenediaminetetraacetates
Author(s) -
Janicki Rafał,
Mondry Anna
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300089
Subject(s) - chemistry , ethylenediaminetetraacetic acid , luminescence , denticity , phosphonate , context (archaeology) , monomer , lanthanide , crystallography , crystal structure , quantum yield , inorganic chemistry , nuclear chemistry , chelation , stereochemistry , ion , organic chemistry , paleontology , physics , optoelectronics , biology , polymer , quantum mechanics , fluorescence
The structural and spectroscopic properties of the Nd 3+ compounds [C(NH 2 ) 3 ] 7 [Nd(EDTMP)(CO 3 )] · 10H 2 O, K 17 H 3 [Nd 4 (EDTMP) 4 ] · 36H 2 O, [C(NH 2 ) 3 ][Nd(EDTA)(H 2 O) 3 ] and Na[Nd(EDTA)(H 2 O) 3 ]·5H 2 O are presented (H 4 EDTA = ethylenediaminetetraacetic acid, H 8 EDTMP is a phosphonic acid analogue of H 4 EDTA). The obtained monomeric [Nd(EDTMP)(CO 3 )] 7– and tetrameric [Nd 4 (EDTMP) 4 ] 20– structures, in which bidentate carbonate and tridentate bridged phosphonate coordination patterns appear, are exceptional. The use of different countercations has allowed us to assess their role in crystal formation and their influence on the spectroscopic properties of the investigated crystals. The countercations slightly change the geometry of [Nd(EDTA)(H 2 O) 3 ] – and some subtle modifications of the geometry of the carboxylic groups is observed. These changes are discussed in the context of hypersensitive transition intensities. The intensities of the f–f transitions in all studied crystals were determined and analyzed basing on the Judd–Ofelt theory. Luminescence of the Nd 3+ ions in the NIR region could be observed solely in the phosphonate complexes. The luminescence quantum yields were calculated from the luminescence lifetimes and the Judd–Ofelt parameters. The Φ value for the rigid tetramer [Nd 4 (EDTMP) 4 ] 20– is twice as large (7 %) as that for the monomer [Nd(EDTMP)(CO 3 )] 7– (3.5 %).