Theoretical investigation of the lack of chiral self-sorting behaviour of a molecular cinquefoil knot

Despite the profound implications of chiral self-sorting in various fields such as biology, materials, catalysis, and supramolecular chemistry, the elucidation of intrinsic factors that affect the efficiency of this process remains a formidable challenge. Here, we present a theoretical analysis based on a recent example of a molecular cinquefoil knot. By introducing various amino acids into the chiral ligands, we probe the potential factors contributing to the absence of chiral self-sorting. Energy profile shows that the thermodynamic stability of the diastereoisomeric helicates is considerably influenced by the ratio and arrangement of chiral ligands. From our calculations, the interaction strength linked to chiral ligands exerts a greater influence on determining the chiral self-sorting outcome compared to structural or steric effects. A better understanding of the mechanism of chiral self-sorting formation of circular helicates could aid in the design of topologically chiral molecules with diverse functionalities.