THE NATURE OF PI-PI INTERACTIONS
THE NATURE OF PI-PI INTERACTIONS
复制标题
DOI：
10.1021/ja00170a016
复制
发表时间：
1990-07-04
影响因子：
15
通讯作者：
SANDERS, JKM
中科院分区：
文献类型：
--
作者：
HUNTER, CA;SANDERS, JKM
用一个简单的π-体系电荷分布模型解释了芳香族分子间相互作用的强烈几何要求。该模型的主要特点是，它分别考虑了σ-骨架和π-电子，并证明了净有利的π-π。相互作用实际上是.pi-.pi的结果。相互作用实际上是？的结果。能战胜圆周率的吸引力。-圆周率。排斥力。这些计算与对卟啉.pi-.pi的观测相关联。溶液和结晶态的相互作用。通过使用一个理想化的π原子，给出了预测有利的π原子几何形状的一些一般规则。相互作用是衍生出来的。特别是，预测了有利的偏移量或滑动的几何图形。这些规则成功地预测了芳香族分子晶体结构中分子间相互作用的几何形状，并使一系列主客体现象合理化。该理论表明，电子给体-受体(EDA)的概念可能具有误导性：重要的是分子间接触点上原子的性质，而不是整个分子的性质。
A simple model of the charge distribution in a .pi.-system is used to explain the strong geometrical requirements for interactions between aromatic molecules. The key feature of the model is that it considers the .sigma.-framework and the .pi.-electrons separately and demonstrates that net favorable .pi.-.pi. interactions are actually the result of .pi.-.pi. interactions are actually the result of .pi.-.sigma. attractions that overcome .pi.-.pi. repulsions. The calculations correlate with observations made on porphyrin .pi.-.pi. interactions both in solution and in the crystalline state. By using an idealized .pi.-atom, some general rules for predicting the geometry of favorable .pi.-.pi. interactions are derived. In particular a favorable offset or slipped geometry is predicted. These rules successfully predict the geometry of intermolecular interactions in the crystal structures of aromatic molecules and rationalize a range of host-guest phenomena. The theory demonstrates that the electron donor-acceptor (EDA) concept can be misleading: it is the properties of the atoms at the points of intermolecular contact rather than the overall molecular properties which are important.