Complex Chiral Induction Processes at the Solution/Solid Interface.

Abstract

Two-dimensional supramolecular chirality is often achieved by confining molecules against a solid surface. The sergeants–soldiers principle is a popular strategy to fabricate chiral surfaces using predominantly achiral molecules. In this method, achiral molecules (the soldiers) are forced to assemble in a chiral fashion by mixing them with a small percentage of structurally similar chiral molecules (the sergeants). The full complexity of the amplification processes in chiral induction studies is rarely revealed due to the specific experimental conditions used. Here we report the evolution of chirality in mixed supramolecular networks of chiral and achiral dehydrobenzo[12]annulene (DBA) derivatives using scanning tunneling microscopy (STM) at the solution/solid interface. The experiments were carried out in the high sergeants–soldiers mole ratio regime in relatively concentrated solutions. Variation in the sergeants/soldiers composition at a constant solution concentration revealed different mole ratio regimes where either amplification of supramolecular handedness as defined by the sergeant chirality or its reversal was observed. The chiral induction/reversal processes were found to be a convolution of different phenomena occurring at the solution-solid interface namely, structural polymorphism, competitive adsorption and adaptive host–guest recognition. Grasping the full complexity of chiral amplification processes as described here is a stepping-stone toward developing a predictive understanding of chiral amplification processes.