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Researchers controlled the self-assembly of a perylene bisimide (PBI) molecule into three distinct 1D supramolecular polymorphs. This control over molecular packing arrangements was achieved through physical or chemical methods, offering insights into polymorphism.

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Area of Science:

  • Materials Science
  • Supramolecular Chemistry
  • Physical Chemistry

Background:

  • Controlling polymorphism in molecular solids is crucial as properties depend on molecular packing.
  • Perylene bisimide (PBI) derivatives are widely studied for their optoelectronic properties.

Purpose of the Study:

  • To investigate the self-assembly of a PBI organogelator (PBI-4) into distinct one-dimensional (1D) supramolecular polymorphs.
  • To understand the factors governing the formation and interconversion of these polymorphs.

Main Methods:

  • UV/vis, CD, fluorescence, and IR spectroscopy
  • Atomic Force Microscopy (AFM)
  • Nudged Elastic Band (NEB) calculations
  • Time-, concentration-, and temperature-dependent experiments

Main Results:

  • PBI-4 self-assembled into three distinct 1D supramolecular polymorphs (Agg 1-3) in the same solvent/concentration at room temperature.
  • Polymorphs differ in π-π-stacking and hydrogen-bonding patterns.
  • NEB calculations revealed nucleation pathways involving a kinetically trapped state (Agg 1).
  • Thermodynamic stability and interconversion kinetics were elucidated.

Conclusions:

  • The production of specific polymorphs can be achieved via ultrasonication or seeding.
  • This study advances the understanding of polymorphism in self-assembled 1D structures.