Rusinska-Roszak Danuta
Institute of Chemical Technology and Engineering, Poznan University of Technology, ul. Berdychowo 4, 60-965 Poznan, Poland.
Molecules. 2017 Mar 18;22(3):481. doi: 10.3390/molecules22030481.
Intramolecular hydrogen bonding (HB) is one of the most studied noncovalent interactions of molecules. Many physical, spectral, and topological properties of compounds are under the influence of HB, and there are many parameters used to notice and to describe these changes. Hitherto, no general method of measurement of the energy of intramolecular hydrogen bond (E) has been put into effect. We propose the molecular tailoring approach (MTA) for E calculation, modified to apply it to Ar-O-H∙∙∙O=C systems. The method, based on quantum calculations, was checked earlier for hydroxycarbonyl-saturated compounds, and for structures with resonance-assisted hydrogen bonding (RAHB). For phenolic compounds, the accuracy, repeatability, and applicability of the method is now confirmed for nearly 140 structures. For each structure its aromaticity HOMA indices were calculated for the central () ring and for the quasiaromatic rings given by intramolecular HB. The comparison of calculated HB energies and values of estimated aromaticity indices allowed us to observe, in some substituted phenols and quinones, the phenomenon of transfer of aromaticity from the -ring to the H-bonded ring via the effect of electron delocalization.
分子内氢键（HB）是分子间研究最多的非共价相互作用之一。化合物的许多物理、光谱和拓扑性质都受氢键的影响，并且有许多参数可用于观察和描述这些变化。迄今为止，尚未实施一种通用的测量分子内氢键能量（E）的方法。我们提出了用于计算E的分子剪裁方法（MTA），并对其进行了修改以应用于Ar-O-H∙∙∙O=C体系。该方法基于量子计算，之前已针对羟基羰基饱和化合物以及具有共振辅助氢键（RAHB）的结构进行了检验。对于酚类化合物，该方法的准确性、可重复性和适用性现已在近140种结构中得到证实。对于每种结构，计算了其中心（）环以及由分子内氢键给出的准芳香环的芳香性HOMA指数。计算得到的氢键能量与估计的芳香性指数值的比较使我们能够在一些取代酚和醌中观察到，通过电子离域效应，芳香性从-环转移到氢键环的现象。
