Breakdown of the energy gap law in molecular lanthanoid luminescence: the smallest energy gap is not universally relevant for nonradiative deactivation.
Breakdown of the energy gap law in molecular lanthanoid luminescence: the smallest energy gap is not universally relevant for nonradiative deactivation.
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DOI：
10.1021/ic500017a
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发表时间：
2014-03
影响因子：
4.6
通讯作者：
Christine Doffek;Jessica Wahsner;Elisabeth Kreidt;Michael Seitz
中科院分区：
文献类型：
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作者：
Christine Doffek;Jessica Wahsner;Elisabeth Kreidt;Michael Seitz
几十年来，能隙定律一直是分子配位化学中讨论镧系元素发光非辐射失活的流行理论框架。在这里，我们通过钐和镝模型配合物的实验表明，镧系元素发射态和次低电子态之间的能隙 ΔE 的大小不能被认为是芳香族 C-H 和 C-D 振荡器泛音非辐射失活定量程度的可靠且准确的预测因子。由于能隙是能隙定律整个概念框架的中心支柱，这一发现在很大程度上使该分子多声子弛豫的定量描述理论无效。
For several decades, the energy gap law has been the prevalent theoretical framework for the discussion of nonradiative deactivation of lanthanoid luminescence in molecular coordination chemistry. Here we show experimentally on samarium and dysprosium model complexes that the size of the energy gap ΔE between a lanthanoid emitting state and the next-lower electronic state cannot be considered a reliable and accurate predictor of the quantitative extent of nonradiative deactivation by aromatic C-H and C-D oscillator overtones. Because the energy gap is the central pillar for the entire conceptual framework of the energy gap law, this finding amounts to largely invalidating this theory for the quantitative description of molecular multiphonon relaxation.