Cooperative or anticooperative: how noncovalent interactions influence each other

Abstract

This computational study examines the key factors that control the structures and energetics of the coexistence of multiple noncovalent interactions. 4-Amino-2-iodophenol is taken as a model that exhibits nine different kinds of noncovalent interactions, viz., cation−π (CP), hydrogen bond (HB) through O (OHB), HB through N (NHB), halogen bond (XB), π–π (PP), metal ion–lone pair (ML) through O (OML), ML through N (NML), charge assisted hydrogen bond (CHB) through O (OCHB), and CHB through N (NCHB). Through all possible combinations of these noncovalent interactions, based on energy, geometry, charge, and atoms in molecules (AIM) analysis, we have systematically analyzed the cooperativity among 40 ternary systems and 105 quaternary systems. We have observed that CP–HB, CP–XB, CP–PP, HB–HB, HB–XB, HB–PP, HB–ML, HB–CHB, XB–PP, XB–ML, XB–CHB, PP–ML, and PP–OCHB can form cooperative ternary systems. While studying the quaternary systems, we have observed that HB, XB, and PP work together by enhancing each other’s strength. The study highlights that the positively charged species enhances HB–HB and HB–PP interactions and forms cooperative HB–HB–CHB, HB–HB–ML, HB–PP–ML, and HB–PP–CHB systems. Surprisingly, OHB–OML–NML, OHB–OML–OCHB, OHB–OML–NCHB, OHB–NML–OCHB, NHB–OML–NML, NHB–OML–NCHB, and NHB–NML–OCHB are also cooperative in nature despite the electrostatic repulsion between two positive charge species. The current study shows the widespread presence of cooperativity as well as anticooperativity in supramolecular assembles.