2,2′‐Bipyrimidine as Efficient Sensitizer of the Solid‐State Luminescence of Lanthanide and Uranyl Ions from Visible to Near‐Infrared |
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| Authors: | Gaël Zucchi Dr Olivier Maury Dr Pierre Thuéry Dr Frédéric Gumy Jean‐Claude?G Bünzli Prof?Dr Michel Ephritikhine Dr |
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| Institution: | 1. CEA, IRAMIS, SIS2?M, Laboratoire Claude Fréjacques, CNRS URA 331, 91191 Gif‐sur‐Yvette (France), Fax: (+33)?169‐08‐66‐40;2. Université de Lyon, Laboratoire de Chimie, CNRS‐Ecole Normale Supérieure de Lyon, UMR 5182, 46 allée d'Italie, 69007 Lyon (France);3. Laboratory of Lanthanide Supramolecular Chemistry, école Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland) |
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| Abstract: | Treatment of Ln(NO3)3?nH2O with 1 or 2 equiv 2,2′‐bipyrimidine (BPM) in dry THF readily afforded the monometallic complexes Ln(NO3)3(bpm)2] (Ln=Eu, Gd, Dy, Tm) or Ln(NO3)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(NO3)3(bpm)2]?THF (Ln=Nd, Sm) from THF, or Ln(NO3)3(bpm)(MeOH)2]?MeOH (Ln=Ce, Nd, Sm) from MeOH. Treatment of UO2(NO3)2?6H2O with 1 equiv BPM in THF afforded the monoadduct UO2(NO3)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 YbIII 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. |
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| Keywords: | bipyrimidine lanthanides luminescence sensitizers solid‐state structures |
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