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La adición de azido dependiente de sustitutos a los isocyanuros genera complejos de iridio fuertemente luminiscentes

Chenggang Jiang¹, Louise M Cañada¹, Ngoc Bao Nguyen¹

¹Department of Chemistry, University of Houston, 3585 Cullen Blvd. Room 112, Houston, Texas 77204-5003, United States.

Journal of the American Chemical Society

|January 5, 2023

Resumen

Se sintetizaron nuevos complejos de iridio luminiscentes reaccionando complejos de iridio bis-isocianuro con azido. El resultado de la reacción, que produce cianamido, tetrazolato o estructuras acopladas, depende de los sustituyentes de isocianuro de arilo, que producen materiales altamente luminiscentes.

Área de la Ciencia:

Química organometálica
La fotofísica
Ciencias de los materiales

Sus antecedentes:

La funcionalización centrada en los ligandos proporciona acceso a estructuras organometálicas únicas.
Estas estructuras pueden exhibir nuevas propiedades fotofísicas no alcanzables a través de la química de coordinación tradicional.

Objetivo del estudio:

Para explorar la reacción de los complejos de bis-ciclometalado de iridio bis-isocianuro con azida.
Para sintetizar y caracterizar nuevos compuestos organometálicos luminiscentes.
Investigar la influencia de los sustituyentes de isocianuro de arilo en las vías de reacción y en las propiedades del producto.

Principales métodos:

Síntesis de complejos de bis-ciclometalado de iridio bis-isocianuro.
Reacción de complejos de iridio con azida en condiciones variables.
Caracterización de los productos mediante técnicas espectroscópicas y analíticas.
Mediciones de las propiedades fotofísicas, incluidos los rendimientos cuánticos de la fotoluminiscencia.

Principales resultados:

Las vías de reacción están dictadas por las propiedades electrónicas de los sustituyentes de isocianuro de arilo.
Los grupos de extracción de electrones producen productos de cianamido de arilo (2) mediante extrusión de N2.
Los grupos donantes de electrones conducen a resultados diversos: estructuras de tetrazolato unidas a C (3) a través de la cicloadición [3 + 2], o nuevos ligandos quelantes (4) de fragmentos de tetrazolato y cianamido acoplados.
También se aisló un complejo cyanamido de arilo bimetálico (5).
Todos los compuestos sintetizados exhiben luminiscencia, con altos rendimientos cuánticos (hasta 0,87) para varios colores de emisión.

Conclusiones:

La funcionalización centrada en los ligandos de los complejos de bis-isocianuro de iridio con azido ofrece rutas sintéticas versátiles para nuevos materiales luminiscentes.
Los efectos sustituyentes sobre el ligando isocyanuro son cruciales para controlar el resultado de la reacción y la arquitectura molecular resultante.
Los compuestos sintetizados muestran propiedades fotofísicas prometedoras, destacando su potencial para aplicaciones en tecnologías basadas en la luminiscencia.

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