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PreprintCC BYChemRxiv

Temporal Control of Chiral Selection in Non-Covalent Systems through Kinetically Programmed Threading

  • Hang Zhou1,2,3
  • Xi-Ran Yang2,3
  • Xin-Yu Pang2,3,4
  • Feng Chen1
  • Jiaxing He1
  • David Lee Phillips1
  • Wei Jiang2,3
  • Ho Yu Au-Yeung1,5
5 affiliations
  1. 1Department of Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong, China, 999077
  2. 2Department of Chemistry
  3. 3Southern University of Science and Technology
  4. 4Department of Chemistry, Washington University in St. Louis, One Brookings Drive, Saint Louis, Missouri, 63130
  5. 5HKU-CAS Joint Laboratory on New Materials and State Key Laboratory of Synthetic Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong, China, 999077
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Abstract

While challenging, current methods for achieving stereoselectivity in non-covalent systems are dominated by thermodynamic strategies, leaving the dynamic expression of chiral biases under kinetic control almost unchartered. In this work, a programmable, reversible (pseudo)[2]rotaxane assembly is introduced to realize stereoselectivity under kinetic control. By leveraging the well-defined interlocked structures and threading pathways, not only the structures of the interlocked components can be precisely engineered to create a substantial difference in the activation barriers for kinetic stereoselectivity, but also the exchange rate, and hence lifetime of the kinetically generated chiral bias can be modulated via the thermodynamic stability of the (pseudo)[2]rotaxanes. Furthermore, the mechanically interlocked platform is integrated with the supramolecular encapsulation of a chromophoric guest, and the evolution and decay of the kinetic chiral bias is successfully translated into a readable, time-dependent optical signal. Due to the dynamic nature of the non-covalent and reversible threading, this transient kinetic bias and output can be erased on demand by thermal acceleration of the noncovalent exchange. Ultimately, this strategy introduces a general design paradigm for using mechanical interlocking to achieve precise temporal control over chirality transmission in nonequilibrium supramolecular systems.

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Cite

BibTeXRIS
BibTeX
@misc{zhou2026temporal,
  title = {{Temporal Control of Chiral Selection in Non-Covalent Systems through Kinetically Programmed Threading}},
  author = {Hang Zhou and Xi-Ran Yang and Xin-Yu Pang and Feng Chen and Jiaxing He and David Lee Phillips and Wei Jiang and Ho Yu Au-Yeung},
  howpublished = {ChemRxiv},
  year = {2026},
  month = aug,
  doi = {10.26434/chemrxiv.15008083/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008083/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Temporal Control of Chiral Selection in Non-Covalent Systems through Kinetically Programmed Threading
AU  - Hang Zhou
AU  - Xi-Ran Yang
AU  - Xin-Yu Pang
AU  - Feng Chen
AU  - Jiaxing He
AU  - David Lee Phillips
AU  - Wei Jiang
AU  - Ho Yu Au-Yeung
PY  - 2026
DA  - 2026/08/31
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008083/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008083/v1
AB  - While challenging, current methods for achieving stereoselectivity in non-covalent systems are dominated by thermodynamic strategies, leaving the dynamic expression of chiral biases under kinetic control almost unchartered. In this work, a programmable, reversible (pseudo)[2]rotaxane assembly is introduced to realize stereoselectivity under kinetic control. By leveraging the well-defined interlocked structures and threading pathways, not only the structures of the interlocked components can be precisely engineered to create a substantial difference in the activation barriers for kinetic stereoselectivity, but also the exchange rate, and hence lifetime of the kinetically generated chiral bias can be modulated via the thermodynamic stability of the (pseudo)[2]rotaxanes. Furthermore, the mechanically interlocked platform is integrated with the supramolecular encapsulation of a chromophoric guest, and the evolution and decay of the kinetic chiral bias is successfully translated into a readable, time-dependent optical signal. Due to the dynamic nature of the non-covalent and reversible threading, this transient kinetic bias and output can be erased on demand by thermal acceleration of the noncovalent exchange. Ultimately, this strategy introduces a general design paradigm for using mechanical interlocking to achieve precise temporal control over chirality transmission in nonequilibrium supramolecular systems.
ER  -