Coordination of terpyridine to Li+ in two different ionic liquids.
Coordination of terpyridine to Li+ in two different ionic liquids.
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DOI：
10.1021/ic4020724
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发表时间：
2013-11
影响因子：
4.6
通讯作者：
K. Pokorny;Matthias Schmeisser;F. Hampel;A. Zahl;R. Puchta;R. van Eldik
中科院分区：
文献类型：
--
作者：
K. Pokorny;Matthias Schmeisser;F. Hampel;A. Zahl;R. Puchta;R. van Eldik
在（7）Li NMR实验的基础上，以离子液体[emim][NTf 2]和[emim][ClO 4]为溶剂，研究了Li（+）与三齿氮给体三联吡啶的配位反应。对于两种离子液体，NMR数据暗示[Li（terpy）2]（+）的形成。密度泛函理论计算表明，三联吡啶的部分配位涉及的溶剂阴离子的协调可以排除。与溶液中的研究相反，X射线衍射测量导致了完全不同的结果。在[emim][NTf2]的情况下，发现聚合锂物种[Li（terpy）（NTf2）]n控制该络合物的堆叠，而从[emim][ClO4]生长的晶体显示离散的二聚物种[Li（terpy）（ClO4）]2。然而，这两种结构表明，在固态下，每个锂离子形式上由一个三联吡啶分子和一个溶剂阴离子配位，这表明电荷中和和π堆积主要控制结晶过程。
On the basis of (7)Li NMR experiments, the complex-formation reaction between Li(+) and the tridentate N-donor ligand terpyridine was studied in the ionic liquids [emim][NTf2] and [emim][ClO4] as solvents. For both ionic liquids, the NMR data implicate the formation of [Li(terpy)2](+). Density functional theory calculations show that partial coordination of terpyridine involving the coordination of a solvent anion can be excluded. In contrast to the studies in solution, X-ray diffraction measurements led to completely different results. In the case of [emim][NTf2], the polymeric lithium species [Li(terpy)(NTf2)]n was found to control the stacking of this complex, whereas crystals grown from [emim][ClO4] exhibit the discrete dimeric species [Li(terpy)(ClO4)]2. However, both structures indicate that each lithium ion is formally coordinated by one terpy molecule and one solvent anion in the solid state, suggesting that charge neutralization and π stacking mainly control the crystallization process.