Probing the Limits of the Majority-Rules Principle in a Dynamic Supramolecular Polymer

Abstract

By systematic variation of the chemical structure of benzene-1,3,5-tricarboxamide (BTA) derivatives, the effect of chemical structure on the amplification of chirality was studied and quantified. In combination with temperature-dependent amplification experiments, the limits of the majority-rules principle were also investigated. For all BTA derivatives a high, constant helix reversal penalty was determined, which is related to the intermolecular hydrogen bonds that are present in all studied derivatives. For asymmetrically substituted BTA derivatives an odd-even effect was found in the degree of chiral amplification when changing the position of the stereogenic center with respect to the amide functionality. It was found that the mismatch penalty could be directly related to the number of stereocenters present in the molecules. Increasing this number from one to three resulted in an increase in this energy penalty while leaving the helix reversal penalty unaffected. For the majority-rules principle this implies that a single stereocenter present in the molecule contains sufficient chiral information at the molecular level to result in a chirally amplified state at the supramolecular level. Further evidence that the mismatch penalty is directly related to the number of stereocenters was obtained from mixed majority-rules experiments where two BTA derivatives with different numbers of stereocenters with opposite stereoconfiguration were studied in a majority-rules experiment. Finally, the ultimate limits of chiral amplification for the majority-rules principle were investigated, revealing that, given a certain helix reversal penalty, there is an optimum to which the mismatch penalty can be reduced while also enhancing the degree of chiral amplification. Temperature-dependent majority-rules experiments could indeed confirm these simulations. These findings show the relevance of both energy penalties when trying to enhance the degree of chiral amplification for the majority-rules principle in a one-dimensional helical supramolecular polymer.