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El polimorfismo supramolecular en el autoensamblaje unidimensional por control de la vía cinética

Marius Wehner1,2, Merle Insa Silja Röhr1, Michael Bühler1

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Los investigadores controlaron el autoensamblaje de una molécula de perileno bisimida (PBI) en tres polimorfas supramoleculares 1D distintas. Este control sobre los arreglos de empaque molecular se logró a través de métodos físicos o químicos, que ofrecen información sobre el polimorfismo.

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Área de la Ciencia:

  • Ciencias de los materiales
  • Química supramolecular
  • Química Física

Sus antecedentes:

  • El control del polimorfismo en sólidos moleculares es crucial ya que las propiedades dependen del empaque molecular.
  • Los derivados de perileno bisimida (PBI) son ampliamente estudiados por sus propiedades optoelectrónicas.

Objetivo del estudio:

  • Investigar el autoensamblaje de un organogelador PBI (PBI-4) en distintos polimorfos supramoleculares de una dimensión (1D).
  • Comprender los factores que rigen la formación y la interconversión de estos polimorfos.

Principales métodos:

  • Espectroscopía UV/vis, CD, fluorescencia y infrarroja
  • Microscopía de fuerza atómica (AFM)
  • Cálculos de la banda elástica empujada (NEB)
  • Experimentos dependientes del tiempo, la concentración y la temperatura

Principales resultados:

  • PBI-4 autoensamblado en tres polimorfas supramoleculares 1D distintas (Agg 1-3) en el mismo disolvente/concentración a temperatura ambiente.
  • Los polimorfos difieren en los patrones de apilamiento π-π y de enlace de hidrógeno.
  • Los cálculos del NEB revelaron vías de nucleación que implican un estado cinéticamente atrapado (Agg 1).
  • Se aclaró la estabilidad termodinámica y la cinética de la interconversión.

Conclusiones:

  • La producción de polimorfos específicos se puede lograr a través de la ecografía o la siembra.
  • Este estudio avanza en la comprensión del polimorfismo en estructuras 1D autoensambladas.