Efficient Sensitization of Europium, Ytterbium, and Neodymium Functionalized Tris-Dipicolinate Lanthanide Complexes through Tunable Charge-Transfer Excited States

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• 作者：Anthony D’ ; Alé ; o ; Alexandre Picot ; Andrew Beeby ; J. A. Gareth Williams ; Boris Le Guennic ; Chantal Andraud ; Olivier Maury
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：November 17, 2008
• 年：2008
• 卷：47
• 期：22
• 页码：10258-10268
• 全文大小：495K
• 年卷期：v.47,no.22(November 17, 2008)
• ISSN：1520-510X

文摘

A series of push−pull donor-π-conjugated dipicolinic acid ligands and related tris-dipicolinate europium and lutetium complexes have been prepared. The ligands present broad absorption and emission transitions in the visible spectral range unambiguously assigned to charge-transfer transitions (CT) by means of time-dependent density functional theory calculations. The photophysical properties (absorption, emission, luminescence quantum yield, and lifetime) of the corresponding europium complexes were thoroughly investigated. Solvatochromism and temperature effects clearly confirm that Eu(III) sensitization directly occurs from the ligand CT state. In addition, modulation of the energy of the CT donating state by changing the nature of the donor fragment allows the optimal energy of the antennae for europium sensitization to be determined, and this optimal energy was found to be close to the ⁵D₁ accepting state. Finally, this CT sensitization process has been successfully extended to near-infrared emitters (neodymium and ytterbium).