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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydrogen bonding as a modulator of aromaticity and electronic structure of selected ortho -hydroxybenzaldehyde derivatives
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Hydrogen bonding as a modulator of aromaticity and electronic structure of selected ortho -hydroxybenzaldehyde derivatives

机译：氢键作为所选邻羟基苯甲醛衍生物的芳香性和电子结构的调节剂

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Properties of hydrogen bonds can induce changes in geometric or electronic structure parameters in the vicinity of the bridge. Here, we focused primarily on the influence of intramolecular H-bonding on the molecular properties in selected ortho-hydroxybenzaldehydes, with additional restricted insight into substituent effects. Static models were obtained in the framework of density functional theory at B3LYP/6-311+G(d,p) level. The electronic structure parameters evolution was analyzed on the basis of Atoms In Molecules (AIM) and Natural Bond Orbitals methods. The aromaticity changes related to the variable proton position and presence of substituents were studied using Harmonic Oscillator Model of Aromaticity (HOMA), Nucleus-Independent Chemical Shift (NICS) and AIM-based parameter of Matta and Hernández-Trujillo. Finally, Car-Parrinello molecular dynamics was applied to study variability of the hydrogen bridge dynamics. The interplay between effects of the substitution and variable position of the bridged proton was discussed. It was found that the hydrogen bond energies are ca. 9-10 kcal/mol, and the bridged proton exhibits some degree of penetration into the acceptor region. The covalent character of the studied hydrogen bond was most observable when the bridged proton reached the middle position between the donor and acceptor regions. The aromaticity indexes showed that the aromaticity of the central phenyl ring is strongly dependent on the bridged proton position. Correlations between these parameters were found and discussed. In the applied time-scale, the analysis of time evolution of geometric parameters showed that the resonance strengthening does not play a crucial role in the studied compounds.
机译：氢键的性质会导致桥附近的几何或电子结构参数发生变化。在这里，我们主要关注分子内氢键对所选邻羟基苯甲醛中分子性能的影响，另外对取代基效果的了解也有限。在密度泛函理论的框架下，在B3LYP / 6-311 + G（d，p）级别获得了静态模型。基于分子原子（AIM）和自然键轨道方法分析了电子结构参数的演变。使用芳香族谐波振荡器模型（HOMA），核独立化学位移（NICS）以及Matta和Hernández-Trujillo的基于AIM的参数研究了与可变质子位置和取代基的存在有关的芳香性变化。最后，将Car-Parrinello分子动力学应用于研究氢桥动力学的变异性。讨论了取代效应和桥接质子可变位置之间的相互作用。发现氢键能为约。 9-10 kcal / mol，并且桥接的质子表现出一定程度的渗透进入受体区域。当桥接的质子到达供体和受体区域之间的中间位置时，最容易观察到氢键的共价特征。芳香性指数表明，中心苯环的芳香性强烈取决于桥联的质子位置。找到并讨论了这些参数之间的相关性。在所应用的时间尺度上，对几何参数的时间演化分析表明，共振强化在所研究的化合物中没有关键作用。

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