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2,2′‐Bipyrimidine as Efficient Sensitizer of the Solid‐State Luminescence of Lanthanide and Uranyl Ions from Visible to Near‐Infrared
Author(s) -
Zucchi Gaël,
Maury Olivier,
Thuéry Pierre,
Gumy Frédéric,
Bünzli JeanClaude G.,
Ephritikhine Michel
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901517
Subject(s) - lanthanide , uranyl , luminescence , chemistry , recrystallization (geology) , ion , crystal structure , photochemistry , crystallography , inorganic chemistry , materials science , organic chemistry , paleontology , optoelectronics , biology
Treatment of Ln(NO 3 ) 3 ⋅ n H 2 O with 1 or 2 equiv 2,2′‐bipyrimidine (BPM) in dry THF readily afforded the monometallic complexes [Ln(NO 3 ) 3 (bpm) 2 ] (Ln=Eu, Gd, Dy, Tm) or [Ln(NO 3 ) 3 (bpm) 2 ]⋅THF (Ln=Eu, Tb, Er, Yb) after recrystallization from MeOH or THF, respectively. Reactions with nitrate salts of the larger lanthanide ions (Ln=Ce, Nd, Sm) yielded one of two distinct monometallic complexes, depending on the recrystallization solvent: [Ln(NO 3 ) 3 (bpm) 2 ]⋅THF (Ln=Nd, Sm) from THF, or [Ln(NO 3 ) 3 (bpm)(MeOH) 2 ]⋅MeOH (Ln=Ce, Nd, Sm) from MeOH. Treatment of UO 2 (NO 3 ) 2 ⋅6H 2 O with 1 equiv BPM in THF afforded the monoadduct [UO 2 (NO 3 ) 2 (bpm)] after recrystallization from MeOH. The complexes were characterized by their crystal structure. Solid‐state luminescence measurements on these monometallic complexes showed that BPM is an efficient sensitizer of the luminescence of both the lanthanide and the uranyl ions emitting visible light, as well as of the Yb III ion emitting in the near‐IR. For Tb, Dy, Eu, and Yb complexes, energy transfer was quite efficient, resulting in quantum yields of 80.0, 5.1, 70.0, and 0.8 %, respectively. All these complexes in the solid state were stable in air.