Nonradiative Deactivation of Lanthanoid Excited States by Inner-Sphere Carboxylates.
Nonradiative Deactivation of Lanthanoid Excited States by Inner-Sphere Carboxylates.
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内层羧酸盐对镧系元素激发态的非辐射失活
DOI：
10.1021/acs.inorgchem.5b01920
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发表时间：
2015
影响因子：
4.6
通讯作者：
M. Seitz
中科院分区：
文献类型：
--
作者：
J. Wahsner;M. Seitz
金属中心激发态的振动失活是控制无机发光团发光的基本过程之一。在分子类镧发光中，调节和系统研究这些过程的最可靠方法是X - h拉伸模式（X = O， N， C）的氘化。除了这些高能量振动基元的影响外，对于存在于类镧络合物中的其他振子碎片的影响所知甚少。我们开发了一种合成方案，以稳定的13c /18O同位素在羧酸基上有效和选择性地标记流行的螯合剂基序“吡啶-2-羧酸”。相应的同位素类镧配合物（Ln = Sm, Eu, Ho）在同位素取代后，局部模式羰基伸展频率降低了5%。虽然这似乎对具有中高能间隙的类镧（Sm和Eu）的发光没有任何影响，但我们已经发现了第一个可量化的发光同位素效应的例子，用于钬（3K8→5I5）的近红外跃迁之一，仅涉及四个羰基振荡子的振动环境的同位素编辑。
The vibrational deactivation of metal-centered excited states is one of the fundamental processes that governs the luminescence of inorganic luminophores. In molecular lanthanoid luminescence, the most reliable way to modulate and systematically investigate these processes is deuteration of X–H stretching modes (X = O, N, C). Apart from the effect of these high-energy vibrational motifs, very little is known about the impact of other oscillator fragments present in lanthanoid complexes. We have developed a synthetic protocol to efficiently and selectively label the popular chelator motif “pyridine-2-carboxylic acid” with stable13C/18O isotope at the carboxylate group. The corresponding isotopologic lanthanoid complexes (Ln = Sm, Eu, Ho) show a decrease of the local-mode carbonyl stretching frequency of up to 5% after isotopic substitution. While this does not seems to have any effect on the luminescence of lanthanoids with medium- to high-energy gaps (Sm and Eu), we have found the first example of a quantifiable luminescence isotope effect for one of the near-IR transitions of holmium (3K8→5I5) that only involves the isotopic editing of the vibrational environment at the four carbonyl oscillators.
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全氘化 2,2-联吡啶-6,6-二羧酸酯：溶液中铥发光的极其有效的敏化剂。
影响因子：
4.6
作者：
Jessica Wahsner;Michael Seitz
通讯作者：
Michael Seitz
影响因子：
0.6
作者：
M. Tsvirko;S. Meshkova;V. Venchikov;Z. Topilova;D. V. Bol’shoi
通讯作者：
M. Tsvirko;S. Meshkova;V. Venchikov;Z. Topilova;D. V. Bol’shoi
DOI：
10.1021/jz2006447
发表时间：
2011-06-27
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
Lipkin JS;Song R;Fenlon EE;Brewer SH
通讯作者：
Brewer SH
影响因子：
4.6
作者：
Christine Doffek;Jessica Wahsner;Elisabeth Kreidt;Michael Seitz
通讯作者：
Christine Doffek;Jessica Wahsner;Elisabeth Kreidt;Michael Seitz
影响因子：
2.8
作者：
Hasegawa, Y;Murakoshi, K;Yamanaka, T
通讯作者：
Yamanaka, T