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具有非齿双吡啶配体的镧系（III）配合物的激发态性质。

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand.

机构信息

Université de Lyon, ENS de Lyon, Laboratoire de Chimie, CNRS UMR 5182, Université Claude Bernard Lyon 1, 69342, Lyon, France.

Universität Heidelberg, Anorganisch-Chemisches Institut, INF 270, 69120, Heidelberg, Germany.

出版信息

Chemistry. 2021 Jul 16;27(40):10303-10312. doi: 10.1002/chem.202005459. Epub 2021 May 2.

DOI:10.1002/chem.202005459
PMID:33780569
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8360039/
Abstract

Eu , Tb , Gd and Yb complexes of the nonadentate bispidine derivative L (bispidine=3,7-diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X-ray crystallography reveals full encapsulation by the nonadentate ligand L that enforces to all Ln cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C symmetry). The well-resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long-lived excited states and high emission quantum yields ([Eu L ] , H O, 298 K, τ=1.51 ms, ϕ=0.35; [Tb L ] , H O, 298 K, τ=1.95 ms, ϕ=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.

摘要

成功合成了非齿双吡啶衍生物 L（双吡啶=3,7-二氮杂双环[3.3.1]壬烷）与 Eu、Tb、Gd 和 Yb 的配合物，并研究了它们的发光性质。X 射线晶体学揭示了非齿配体 L 的完全包裹，迫使所有 Ln 阳离子采用共同的高度对称的帽式四方反棱柱（CSAPR）配位几何形状（伪 C 对称性）。在固态和溶液中都能得到良好分辨的相同发射光谱，这证实了两种介质中具有相同的结构。因此，可以预期这些配合物具有长寿命激发态和高发射量子产率（[EuL]，H2O，298 K，τ=1.51 ms，ϕ=0.35；[TbL]，H2O，298 K，τ=1.95 ms，ϕ=0.68）。这些配合物具有非常高的动力学和热力学稳定性，为有趣的生物探针提供了可能的基础。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/81c609b7e4d2/CHEM-27-10303-g015.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/41d1166fcec3/CHEM-27-10303-g012.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/b7b592bacd6e/CHEM-27-10303-g002.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/81c609b7e4d2/CHEM-27-10303-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/9e66a1150ba5/CHEM-27-10303-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/ac81e3855c41/CHEM-27-10303-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/a5def434720c/CHEM-27-10303-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/bddb5f1d04d5/CHEM-27-10303-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/b4e10f7fa7b2/CHEM-27-10303-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/78bcd90f83ae/CHEM-27-10303-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/db9ec6af0f84/CHEM-27-10303-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/b89581347acd/CHEM-27-10303-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/0b456930c8ea/CHEM-27-10303-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/41d1166fcec3/CHEM-27-10303-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/b51cff220a39/CHEM-27-10303-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/b7b592bacd6e/CHEM-27-10303-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/4daf86de0f1f/CHEM-27-10303-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c6bf/8360039/81c609b7e4d2/CHEM-27-10303-g015.jpg

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