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Highly Luminescent Salts Containing Well-Shielded Lanthanide-Centered Complex Anions and Bulky Imidazolium Countercations

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journal contribution
posted on 02.09.2014, 00:00 by Si-Fu Tang, Chantal Lorbeer, Xinjiao Wang, Pushpal Ghosh, Anja-Verena Mudring
Four salts containing imidazolium cations and europium­(III)- or terbium­(III)-centered complex anions have been successfully synthesized from an ethanol/H2O solution. The single-crystal X-ray diffraction analyses reveal that these compounds have a common formula of [R]­[Ln­(DETCAP)4] [R = 1-ethyl-3-methylimidazolium (C2mim), Ln = Eu (1) and Tb (2); R = 1-butyl-3-methylimidazolium (C4mim), Ln = Eu (3) and Tb (4); DETCAP = diethyl-2,2,2-trichloroacetylphosphoramidate], in which the lanthanide centers are chelated by four chelating pseudo-β-diketonate ligands (DETCAP), forming the respective complex anions. Their thermal behaviors and stabilities were also investigated to study the role of the length of the side chain in the cations. Fluorescence measurements at both room temperature and liquid-nitrogen temperature show that these materials show intense characteristic europium­(III) or terbium­(III) emissions and have long decay times. Their overall quantum yields were determined to be in the range of 30–49%.