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La caja verde: un anfitrión macrocíclico de perileno dimida electrónicamente versátil para fullerenos

Timothy A Barendt¹, William K Myers², Stuart P Cornes³

¹Chemistry Research Laboratory, Department of Chemistry , University of Oxford , Mansfield Road , Oxford OX1 3TA , United Kingdom.

Journal of the American Chemical Society

|November 29, 2019

Resumen

Los investigadores desarrollaron la "Caja Verde", un anfitrión de perileno diimida rico en electrones, para el reconocimiento del fullereno. Este sistema permite la transferencia de electrones sintonizables, imitando la fotosíntesis y creando nuevos estados de carga separada.

Área de la Ciencia:

Química supramolecular
Productos electrónicos orgánicos
La fotoquímica

Sus antecedentes:

Los fullerenos son aceptores de electrones clave en los sistemas biomiméticos, que modelan la fotosíntesis natural.
Las diimidas de perileno (PDIs) suelen ser deficientes en electrones, lo que dificulta su uso en sistemas de reconocimiento de fullereno.
El diseño de PDIs ricos en electrones es crucial para crear díadas donantes-aceptantes favorables.

Objetivo del estudio:

Sintetizar un nuevo huésped macrocíclico utilizando unidades PDI ricas en electrones para el reconocimiento del fullereno.
Investigar las interacciones electrónicas y la dinámica de transferencia de electrones entre el huésped y los huéspedes de fullereno.
Explorar la comunicación electrónica ajustable al disolvente en sistemas supramoleculares basados en el fullereno.

Principales métodos:

Síntesis de un gran receptor macrocíclico (
Caja verde
) compuesto por paneles de bispirrolidina PDI ricos en electrones.
Caracterización espectroscópica que incluye absorción electrónica, emisión de fluorescencia, RMN, EPR con resolución en el tiempo y espectrometría de masas.
Análisis electroquímico mediante voltametría cíclica y estudios computacionales mediante DFT.

Principales resultados:

La Caja Verde reconoce efectivamente los fullerenos (C_60/70) a través de interacciones no covalentes.
La transferencia parcial de carga ocurre en disolventes de baja polaridad, mientras que la transferencia completa de electrones para formar un par de iones radicales se logra en disolventes de alta polaridad.
El estado separado de carga exhibe reversibilidad termodinámica y estabilidad cinética.
Se ha demostrado una comunicación electrónica intermolecular sin precedentes con los fullerenos.

Conclusiones:

La Caja Verde es un anfitrión pionero que utiliza PDIs ricos en electrones para el reconocimiento del fullereno.
Este sistema permite el control de la transferencia de electrones, cerrando la brecha entre la química huésped-huésped y la electrónica orgánica.
La capacidad de ajustar los estados de transferencia de carga ofrece nuevas vías para el diseño de materiales funcionales avanzados.

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