Tiwari Mrityunjay K, Vanka Kumar
Physical and Material Chemistry Division , CSIR-National Chemical Laboratory , Dr. Homi Bhabha Road, Pashan , Pune-411008 , Maharashtra , India . Email:
Chem Sci. 2017 Feb 1;8(2):1378-1390. doi: 10.1039/c6sc03642b. Epub 2016 Oct 11.
It has been well established that long range secondary electrostatic interactions (SEIs) have a significant effect on the stability of supramolecular complexes. However, general rules for exploiting SEIs in the rational design of diverse supramolecular complexes have been difficult to obtain. In this work, we outline a quantum chemical approach for understanding the strength of electrostatic interactions. This approach is seen to provide excellent correlation between the electrostatic force and the binding energy between two partners in hydrogen-bonded complexes, as well as that between two ions in ion-pair complexes. Furthermore, we illustrate how the understanding of the binding allows for the rational design of new complexes where the association constant between the two partners can be increased or decreased, as desired, by several orders of magnitude. Hence, the current work showcases a general, simple and powerful method of understanding and exploiting long range secondary electrostatic interactions.
长期以来，人们已经充分认识到长程二级静电相互作用（SEIs）对超分子复合物的稳定性有显著影响。然而，在合理设计各种超分子复合物时利用SEIs的一般规则却难以获得。在这项工作中，我们概述了一种用于理解静电相互作用强度的量子化学方法。这种方法被认为在氢键复合物中两个伙伴之间的静电力与结合能之间，以及离子对复合物中两个离子之间提供了极好的相关性。此外，我们说明了对结合的理解如何有助于合理设计新的复合物，其中两个伙伴之间的缔合常数可以根据需要增加或减少几个数量级。因此，当前的工作展示了一种理解和利用长程二级静电相互作用的通用、简单且强大的方法。
