Hydrogen Bonding Directed Supramolecular Polymerisation of Oligo(Phenylene‐Ethynylene)s: Cooperative Mechanism, Core Symmetry Effect and Chiral Amplification

Abstract

The design of supramolecular motifs with tuneable stability and adjustable supramolecular polymerisation mechanisms is of crucial importance to precisely control the properties of supramolecular assemblies. This report focuses on constructing π-conjugated oligo(phenylene ethynylene) (OPE)-based one-dimensional helical supramolecular polymers that show a cooperative growth mechanism. Thus, a novel set of discotic molecules comprising a rigid OPE core, three amide groups, and peripheral solubilising wedge groups featuring C(3) and C(2) core symmetry was designed and synthesised. All of the discotic molecules are crystalline compounds and lack a columnar mesophase in the solid state. In dilute methylcyclohexane solution, one-dimensional supramolecular polymers are formed stabilised by threefold intermolecular hydrogen bonding and π-π interactions, as evidenced by (1)H NMR measurements. Small-angle X-ray and light scattering measurements reveal significant size differences between the columnar aggregates of C(3)- and C(2)-symmetrical discotics, that is, the core symmetry strongly influences the nature of the supramolecular polymerisation process. Temperature-dependent CD measurements show a highly cooperative polymerisation process for the C(3)-symmetrical discotics. In contrast, the self-assembly of C(2)-symmetrical discotics shows a smaller enthalpy release upon aggregation and decreased cooperativity. In all cases, the peripheral stereogenic centres induce a preferred handedness in the columnar helical aggregates. Moreover, one stereogenic centre suffices to fully bias the helicity in the C(2)-symmetrical discotics. Finally, chiral amplification studies with the C(3)-symmetrical discotics were performed by mixing chiral and achiral discotics (sergeants-and-soldiers experiment) and discotics of opposite chirality (majority-rules experiment). The results demonstrate a very strong sergeants-and-soldiers effect and a rather weak majority-rules effect.