Infrared spectroscopy of multiply charged metal ions: methanol-solvated divalent manganese 18-crown-6 ether systems.
Infrared spectroscopy of multiply charged metal ions: methanol-solvated divalent manganese 18-crown-6 ether systems.
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多电荷金属离子的红外光谱：甲醇溶剂化的二价锰18-冠-6醚体系。
DOI：
10.1021/jp902381y
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
J. Lisy
中科院分区：
文献类型：
--
作者：
Jason D. Rodriguez;J. Lisy
我们开发了一种电声喷雾电离源，可以在气相中成功生成二价 Mn(2+)(18-crown-6)(CH(3)OH)(1-3) 配合物。使用红外预解离光谱在 CH 和 OH 拉伸区域以及密度泛函理论计算对这些配合物进行了研究。为了解决由于 CH(3)OH 和 18-crown-6 CH 拉伸模式以及强烈扰动的 OH 拉伸模式导致的 CH 拉伸区域重叠带的复杂性，我们使用 d(1) 和 d(4) 甲醇替代。对于 n = 1，Mn(2+)...18-crown-6 几何形状与其气相中性构型高度扭曲，以便最大化 18-crown-6 大环氧和 Mn(2+) 之间的有利静电相互作用。对于 n = 2 和 3，CH(3)OH...CH(3)OH 和 CH(3)OH...18-crown-6 相互作用与 Mn(2+)...18-crown-6 相互作用竞争，强烈的氢键 OH 拉伸模式移动超过 500 cm(-1) 至较低频率所证明。
We have developed an electrosonic spray ionization source to successfully generate divalent Mn(2+)(18-crown-6)(CH(3)OH)(1-3) complexes in the gas phase. These complexes have been investigated using infrared predissociation spectroscopy in both the CH and OH stretching regions and with density functional theory calculations. To resolve complications from overlapping bands in the CH stretching region due to CH(3)OH and 18-crown-6 CH stretching modes along with strongly perturbed OH stretching modes, we have used d(1) and d(4) methanol substitution. For n = 1, the Mn(2+)...18-crown-6 geometry is highly distorted from its gas-phase neutral configuration in order to maximize favorable electrostatic interactions between the 18-crown-6 macrocyclic oxygens and Mn(2+). For n = 2 and 3, CH(3)OH...CH(3)OH and CH(3)OH...18-crown-6 interactions compete with the Mn(2+)...18-crown-6 interaction, as evidenced by intense hydrogen-bonded OH stretching modes shifted over 500 cm(-1) to lower frequency.