What Molecular Features Govern the Mechanism of Supramolecular Polymerization?

Abstract

A molecular dilemma! The assigning of mechanisms of supramolecular polymerization based on molecular features is presented. It is conjectured that long-range interactions along the growth direction result in a cooperative mechanism and a lack thereof in an isodesmic pathway (see picture). The former can arise from intermolecular hydrogen bonding along the stack direction.An understanding of the mechanisms of supramolecular polymerization from a molecular point of view is lacking. Several reports in the literature on the mechanism exhibited by different classes of molecules are examined in an attempt to correlate the molecular features to the aggregation pathway followed. It is proposed that long-range interactions between oligomers could lead to their cooperative growth. The lack thereof leads to isodesmicity.