Abstract

Cation–\(\uppi \) or cation–2\(\uppi \) interactions generally exist between one cation and one or two electron-rich \(\uppi \)-ring, which play an important role in many areas (such as benzene, borazine, aromatic rings, graphene and carbon nanotubes). Here, we report the interaction of M-BZ, M(\(\hbox {H}_{{2}}\hbox {O}\))-BZ, M-2BZ and M(\(\hbox {H}_{{2}}\hbox {O}\))-2BZ (\(\hbox {BZ} = \hbox {borazine}\), \(\hbox {M} =\hbox {Li}^{{+}}\), \(\hbox {Na}^{{+}}\), \(\hbox {K}^{{+}}\), \(\hbox {Mg}^{{2+}}\), \(\hbox {Ca}^{{2+}})\) at the B3LYP-D3/TZ2P levels of theory. We found that the interaction energy decreases as the radii of the cations increase. The total interaction energy was decomposed into the dispersion correction, Pauli repulsion, electrostatic interaction and orbital interaction by using energy decomposition analysis. In addition, the binding energy of M-BZ (2BZ) is similar to that of M-benzene (2benzene), indicating the special importance of M-BZ (2BZ) interaction in biological system. From the extended transition state scheme with the theory of natural orbitals for chemical valence, the first dominant deformation densities plot shown the flow of charge between the fragments, which mean the BZ is \(\uppi \) donation and cation (M(\(\hbox {H}_{{2}}\hbox {O}\))) is \(\upsigma \) or \(\uppi \) acceptor.

GraphicAbstract

中文翻译：

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M-BZ，M（$$ \ hbox {H} _ {{2}} \ hbox {O} $$ H 2 O）-BZ，M-2BZ和M（$$ \ hbox {H} _ {{2}} \ hbox {O} $$ H 2 O）-2BZ（$$ \ hbox {M} = \ hbox {Li} ^ {+} $$ M = Li +，$$ \ hbox {Na} ^ {+} $$ Na +，$$ \ hbox {K} ^ {+} $$ K +，$$ \ hbox {Mg} ^ {2 +} $$ Mg 2 +，$$ \ hbox {Ca} ^ {2 +} $$ Ca 2 +）：EDA和ETS-NOCV方法

摘要

阳离子\（\ uppi \）或阳离子2 \（\ uppi \）相互作用通常一个阳离子和一个或两个电子富人之间存在\（\ uppi \） -环，这在许多领域发挥着重要作用（如如苯，硼嗪，芳环，石墨烯和碳纳米管）。在这里，我们报告了M-BZ，M（\（\ hbox {H} _ {{2}} \ hbox {O} \））-BZ，M-2BZ和M（\（\ hbox {H} _ {{2}} \ hbox {O} \））-2BZ（\（\ hbox {BZ} = \ hbox {borazine} \），\（\ hbox {M} = \ hbox {Li} ^ {{+ }} \），\（\ hbox {Na} ^ {{+}} \），\（\ hbox {K} ^ {{++}} \），\（\ hbox {Mg} ^ {{2+} } \），\（\ hbox {Ca} ^ {{2 +}}）\）在B3LYP-D3 / TZ2P的理论水平上。我们发现，相互作用能随着阳离子半径的增加而减小。通过能量分解分析将总相互作用能分解为色散校正，保利排斥，静电相互作用和轨道相互作用。此外，M-BZ（2BZ）的结合能与M-苯（2苯）的结合能相似，这表明M-BZ（2BZ）相互作用在生物系统中特别重要。从扩展的过渡态方案和化学价的自然轨道理论出发，第一主变形密度图显示了碎片之间的电荷流，这意味着BZ是\（\ uppi \）捐赠和阳离子（M（\（ \ hbox {H} _ {{2}} \ hbox {O} \）））是\（\ upsigma \）或\（\ uppi \）接受器。

图形摘要