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Updated: Aug 5, 2026

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
Published on: August 2, 2012
Local Solvent Ordering Drives Supramolecular Chirality Inversion
Triza Pal1, Akta Singh2, Subinoy Adhikari2
1Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Kolkata, India.
Local solvent organization directly controls supramolecular chirality, reversing helical sense in L-phenylalanine perylene bisimide (L-PhePBI) assemblies. This stereomutation is driven by solvent-induced changes in molecular packing and hydrogen bonding, not bulk properties.
Area of Science:
- Supramolecular Chemistry
- Materials Science
- Chemical Physics
Background:
- Supramolecular chirality is typically assumed to be indirectly influenced by solvent bulk properties like polarity.
- The direct impact of local solvent organization on chiral pathway selection remains poorly understood.
Purpose of the Study:
- To investigate the direct role of local solvent organization in dictating supramolecular chirality.
- To demonstrate how solvent composition can precisely control and invert supramolecular helicity.
Main Methods:
- Synthesized a chiral perylene bisimide with L-phenylalanine substituents (L-PhePBI).
- Studied L-PhePBI in water/DMSO mixtures with varying compositions using spectroscopy.
- Employed molecular dynamics simulations to analyze solvent organization and molecular interactions.
- Utilized variable-temperature studies to probe chiral state stability and transitions.
Main Results:
- Complete reversal of helical sense observed in L-PhePBI within a narrow solvent composition range (Δfwater = 0.2).
- Polarity and aggregation levels remained similar, excluding bulk solvent effects.
- Molecular dynamics revealed solvent-dependent hydration shell reorganization influencing molecular twist angles and chiral pathways.
- Thermal inversion identified a kinetically trapped state converting to a stable enantiomorph via hydrogen bond redistribution.
Conclusions:
- Local solvent organization directly dictates supramolecular stereomutation and helicity.
- Solvent composition acts as a precise control parameter for programming chiral organization in supramolecular materials.
- Established a mechanistic link between local solvent ordering, noncovalent interactions, and supramolecular stereomutation.
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