The confluence of structure and dynamics in lanthanide(III) chelates: how dynamics help define structure in solution.
The confluence of structure and dynamics in lanthanide(III) chelates: how dynamics help define structure in solution.
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镧系元素 (III) 螯合物的结构和动力学的汇合：动力学如何帮助定义溶液中的结构。
DOI：
10.1039/c3dt52143e
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
Woods,Mark
中科院分区：
文献类型：
--
作者：
Webber,BenjaminC;Woods,Mark
配位交换过程倾向于主导镧系元素螯合物的溶液状态行为，并且通常禁止小的构象变化的研究。在这篇文章中，我们利用协调刚性Eu 3+螯合物检查小的构象变化，发生在这些螯合物中的水解离交换内外的内部协调领域。结果表明，螯合物的时均构象随水交换速率的增加而改变。这种构象变化反映了螯合物的水合状态（q/rLnH 6）的变化。水化状态最近被表示为两个单独的参数q和rLnH。然而，这两个参数同时描述了相同的结构考虑，在解决方案中是不可区分的，内在相关的，并依赖于，解离水交换速率。这一认识导致更广泛的理解，一个解决方案的状态结构只能通过参考系统的动态来理解。
Coordination exchange processes tend to dominate the solution state behaviour of lanthanide chelates and generally prohibit the study of small conformational changes. In this article we take advantage of coordinatively rigid Eu3+ chelates to examine the small conformational changes that occur in these chelates as water dissociatively exchanges in and out of the inner coordination sphere. The results show that the time-averaged conformation of the chelate alters as the water exchange rate increases. This conformational change reflects a change in the hydration state (q/rLnH6) of the chelate. The hydration state has recently come to be expressed as two separate parameters q and rLnH. However, these two parameters simultaneously describe the same structural considerations which in solution are indistinguishable and intrinsically related to, and dependent upon, the dissociative water exchange rate. This realization leads to the broader understanding that a solution state structure can only be appreciated with reference to the dynamics of the system.