Characterization of highly unusual NH+-O hydrogen bonding to ester ether oxygen atoms through spectroscopic and computational studies.
Characterization of highly unusual NH+-O hydrogen bonding to ester ether oxygen atoms through spectroscopic and computational studies.
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通过光谱和计算研究表征极不寻常的 NH -O 氢键与酯醚氧原子的键合。
DOI：
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发表时间：
2012
影响因子：
2.9
通讯作者：
T. Lectka
中科院分区：
文献类型：
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作者：
M. Scerba;Andrew F. DeBlase;S. Bloom;T. Dudding;Mark A. Johnson;T. Lectka
我们描述了一个非常不寻常的，带电的NH-O氢键，形成在8-（二甲氨基）萘-1-醇酯中，其中铵离子作为分子内氢键供体，在空间上接近酯醚氧原子。对酯羰基频率的红外光谱分析表明，当乙醚氢键可能发生时，显著的蓝移，与更常见的观察到的氢与酯羰基氧成键时发生的红移形成鲜明对比。连接的固有行为（即消除了反离子和溶剂效应）是由分离的气相阳离子与弱结合D(2)分子络合的振动预解离光谱提供的。
We characterize a highly unusual, charged NH-O hydrogen bond formed within esters of 8-(dimethylamino)naphthalen-1-ol in which an ammonium ion serves as an intramolecular hydrogen bond donor to spatially proximate ester ether oxygen atoms. Infrared spectroscopic analysis of the ester carbonyl frequencies demonstrates significant blue-shifting when ether hydrogen bonding is possible, in stark contrast to the more commonly observed red shift that occurs upon hydrogen bonding to the ester carbonyl oxygen. The intrinsic behavior of the linkage (i.e., in which counterions and solvent effects are eliminated) is provided by vibrational predissociation spectroscopy of the isolated gas-phase cations complexed with weakly bound D(2) molecules.