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Formación selectiva de la red conductiva por oxidación inducida por radicales

Jin Young Koo¹, Yumi Yakiyama¹, Gil Ryeong Lee¹

¹The Division of Advanced Materials Science, Pohang University of Science and Technology (POSTECH) , 77 Cheongam-ro, Namgu, Pohang 790-784, Korea.

Journal of the American Chemical Society

|January 28, 2016

Resumen

Un ligando redox activo forma redes de coordinación distintas basadas en Cd. Los radicales traza del ligando inducen redes conductoras de electrones, mientras que el aislamiento conduce a redes no conductoras, revelando un mecanismo de oxidación único.

Área de la Ciencia:

Química de coordinación
Ciencias de los materiales
Productos electrónicos orgánicos

Sus antecedentes:

Las redes de coordinación ofrecen propiedades sintonizables para diversas aplicaciones.
Los ligandos redox-activos pueden introducir características electrónicas y estructurales únicas.
El control del ensamblaje de ligandos es crucial para la funcionalidad de la red.

Objetivo del estudio:

Para sintetizar selectivamente las redes de coordinación basadas en Cd utilizando un ligando redox activo.
Investigar la influencia de las especies de radicales ligandos en la estructura y la conductividad de la red.
Para aclarar el mecanismo de oxidación del ligando dentro de la red de coordinación.

Principales métodos:

Síntesis selectiva de las redes de coordinación basadas en CD.
Utilizando el 2,5,8-tri ((4-piridil) 1,3-diazafenaleno (TPDAP) como un ligando redox activo.
Caracterización de las estructuras de red y las propiedades electrónicas en condiciones variables (presencia o ausencia del radical TPDAP).

Principales resultados:

Formación de redes de coordinación basadas en CD que contengan canales.
Redes conductoras de electrones con estructuras columnares de TPDAP de apilamiento π-π formadas en presencia de radicales de TPDAP (1(•)).
Las redes no conductoras con unidades de dímeros TPDAP se forman en ausencia de radicales TPDAP.
La dimerización de TPDAP aumentó el nivel de HOMO, facilitando la formación de radicales adicionales.

Conclusiones:

Una pequeña cantidad de radical TPDAP inicia un mecanismo de oxidación único.
El ensamblaje de TPDAP en dímeros dentro de la red de coordinación es clave para sus propiedades electrónicas.
Este estudio pone de relieve la importancia de las especies radicales en el control de la estructura y la conductividad de las redes de coordinación.

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