Optical Response of Terpyridine Ligands to Zinc Binding: A Close Look at the Substitution Effect by Spectroscopic Studies at Low Temperature.
Optical Response of Terpyridine Ligands to Zinc Binding: A Close Look at the Substitution Effect by Spectroscopic Studies at Low Temperature.
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DOI：
10.1021/acs.jpcb.6b00515
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发表时间：
2016-04-07
期刊：
影响因子：
--
通讯作者：
Pang Y
中科院分区：
文献类型：
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作者：
Bi X;Pang Y
三吡啶（tpy）配体是结合金属离子的常用构件。合成了几种不同取代基的tpy配体，并对其与锌阳离子的结合进行了研究。研究发现，锌结合诱导的荧光猝灭存在较大的取代基效应。在液氮杜瓦瓶的帮助下，tpy分子被冻结到它们的基态构象，防止（或最小化）光诱导激发态中的分子重组。这使我们能够从局部激发态（具有最小的电荷转移相互作用）和温度依赖性荧光中检测荧光光谱。低温下的荧光响应提供了分子内电荷转移（ICT）相互作用的有用信息。此外，强供体取代基（如Me2N）在观察到的荧光猝灭中起重要作用。该研究也为低温荧光光谱分析ICT机理提供了有益的实例。
Terpyridine (tpy) ligands are popular building blocks to bind metal ions. Several tpy ligands with different substituents were synthesized and examined for their binding with zinc cation. The study revealed a large substituent effect on the zinc binding-induced fluorescence quenching. With the aid of a liquid nitrogen Dewar, the tpy molecules were frozen to their ground-state conformation, preventing (or minimizing) molecular reorganization in the photoinduced excited state. This allowed us to detect the fluorescence spectra from the locally excited state (having a minimum of charge transfer interaction) and the temperature-dependent fluorescence. The fluorescence response to low temperature provided useful information about the intramolecular charge transfer (ICT) interaction between the donor and acceptor groups. Furthermore, a strong donor substituent (such as Me2N) played an essential role in observed fluorescence quenching. The study also provides a useful example to elucidate the ICT mechanism by using low-temperature fluorescence spectroscopy.