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

ABSTRACT

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.

GRAPHICAL ABSTRACT

KEYWORDS:

• Chiral self-sorting
• pentameric circular helicates
• molecular nanotopology

Acknowledgments

L.Z. thanks the East China Normal University, Shanghai Frontiers Science Center of Molecular Intelligent Synthesis, National Natural Science Foundation of China (22001074) and Natural Science Foundation of Shanghai (22ZR1479400) and Z.-H.Z. thanks NSFC Young Scientist Fund (22301080) for financial support.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Author contributions

Z.-H.Z., T.Z. and L.Z. planned the work. X.Z. performed the simulation. X.Z., Y.R. and Z.-H.Z. analysed the data. L.Z. directed the research. All authors contributed to the writing of the manuscript.

Data availability statement

Supplementary information is available for this paper at https://www.tandfonline.com/

Correspondence and requests for materials should be addressed to L.Z.

Supplementary material

Supplemental data for this article can be accessed online at https://doi.org/10.1080/10610278.2024.2335242

Additional information

Funding

This work was funded by the National Natural Science Foundation of China [22001074, 22222303, 22173032] and Natural Science Foundation of Shanghai [22ZR1479400].