Local Solvent Ordering Drives Supramolecular Chirality Inversion
- 1Department of Chemical Sciences Indian Institute of Science Education and Research (IISER) Kolkata India
- 2Tata Institute of Fundamental Research Hyderabad Telangana India
Abstract
Solvent composition is widely assumed to influence supramolecular chirality indirectly through bulk properties such as polarity or solvophobicity. Here, we show that local solvent organization can directly dictate chiral pathway selection and invert supramolecular helicity. A chiral perylene bisimide bearing L‐phenylalanine substituents (L‐PhePBI) undergoes a complete reversal of helical sense in water/DMSO mixtures upon a narrow change in solvent composition (Δf water = 0.2), despite maintaining a similar degree of aggregation. The comparable polarity of the two solvent compositions excludes bulk solvent effects as the origin of this stereomutation. Molecular dynamics simulations reveal that solvent‐composition‐dependent reorganization of the first hydration shell biases molecular twist angles within stacked assemblies, thereby selecting opposite chiral pathways. Variable‐temperature spectroscopic studies further identify a kinetically trapped chiral state that irreversibly converts to a thermodynamically stable enantiomorph upon heating. This thermal inversion is associated with a redistribution of hydrogen bonding from nearest‐neighbor to nonadjacent molecular pairs, stabilizing a distinct packing motif. Together, these results establish a direct mechanistic link between local solvent ordering, noncovalent interaction reorganization, and supramolecular stereomutation, demonstrating solvent composition as a precise control parameter for programming chiral organization in supramolecular materials.
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BibTeX
@article{pal2026local,
title = {{Local Solvent Ordering Drives Supramolecular Chirality Inversion}},
author = {Triza Pal and Akta Singh and Subinoy Adhikari and Jagannath Mondal and Debangshu Chaudhuri},
journal = {Advanced Science},
year = {2026},
month = aug,
doi = {10.1002/advs.76943},
url = {https://doi.org/10.1002/advs.76943},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Local Solvent Ordering Drives Supramolecular Chirality Inversion
AU - Triza Pal
AU - Akta Singh
AU - Subinoy Adhikari
AU - Jagannath Mondal
AU - Debangshu Chaudhuri
PY - 2026
DA - 2026/08/03
JO - Advanced Science
DO - 10.1002/advs.76943
UR - https://doi.org/10.1002/advs.76943
AB - Solvent composition is widely assumed to influence supramolecular chirality indirectly through bulk properties such as polarity or solvophobicity. Here, we show that local solvent organization can directly dictate chiral pathway selection and invert supramolecular helicity. A chiral perylene bisimide bearing L‐phenylalanine substituents (L‐PhePBI) undergoes a complete reversal of helical sense in water/DMSO mixtures upon a narrow change in solvent composition (Δf water = 0.2), despite maintaining a similar degree of aggregation. The comparable polarity of the two solvent compositions excludes bulk solvent effects as the origin of this stereomutation. Molecular dynamics simulations reveal that solvent‐composition‐dependent reorganization of the first hydration shell biases molecular twist angles within stacked assemblies, thereby selecting opposite chiral pathways. Variable‐temperature spectroscopic studies further identify a kinetically trapped chiral state that irreversibly converts to a thermodynamically stable enantiomorph upon heating. This thermal inversion is associated with a redistribution of hydrogen bonding from nearest‐neighbor to nonadjacent molecular pairs, stabilizing a distinct packing motif. Together, these results establish a direct mechanistic link between local solvent ordering, noncovalent interaction reorganization, and supramolecular stereomutation, demonstrating solvent composition as a precise control parameter for programming chiral organization in supramolecular materials.
SN - 2198-3844
ER -