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Aromaticidad conmutable de la ftaalocianina a través de la adición aromática nucleofílica reversible a un complejo de

Filipp M Kolomeychuk^1,2, Evgeniya A Safonova², Marina A Polovkova²

¹Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991, Russia.

Journal of the American Chemical Society

|August 23, 2021

Resumen

Los investigadores lograron una adición nucleofílica reversible a un complejo de ftaalocianina, rompiendo y restaurando su aromaticidad. Este descubrimiento abre las puertas para nuevos materiales basados en ftaalocianina con propiedades fotofísicas ajustables.

Área de la Ciencia:

Química inorgánica
Ciencias de los materiales
Química supramolecular

Sus antecedentes:

Las ftaalocianinas (Pcs) son compuestos macrocíclicos versátiles con amplias aplicaciones en catálisis, detección y optoelectrónica.
La modificación de las propiedades electrónicas y estructurales de los Pcs es crucial para el desarrollo de materiales funcionales avanzados.
Los complejos de ftaalocianina con deficiencia de electrones ofrecen vías de reactividad únicas para el ajuste estructural y de propiedades.

Objetivo del estudio:

Investigar la reactividad de los complejos de fósforo catiónico con déficit de electrones (V) hacia la adición nucleofílica.
Explorar las consecuencias estructurales y fotofísicas de la alteración reversible de la aromaticidad en las ftaalocianinas.
Demostrar el potencial para la creación de nuevos compuestos y materiales intercambiables basados en PC.

Principales métodos:

Síntesis y caracterización del fósforo catiónico deficiente en electrones ((V) complejo de ftaalocianina [PcP ((OMe)) ].
Investigación de las reacciones de adición nucleofílica utilizando hidróxido de potasio (KOH).
Elucidación estructural mediante difracción de rayos X monocristalino, ESI HRMS, RMN y espectroscopia UV.
Análisis computacional utilizando el modelado químico cuántico.

Principales resultados:

La primera observación de adición nucleofílica reversible a un núcleo de ftaalocianina en el complejo [PcP(OMe) 2].
Formación de un adducto no aromático tras la reacción con KOH, con un grupo OH en un carbono α-pirrólico.
Restauración de la aromaticidad y recuperación del complejo inicial tras el tratamiento ácido.
Cambios significativos en las propiedades fotofísicas asociadas con el cambio de aromaticidad reversible.

Conclusiones:

El estudio demuestra una nueva vía para manipular la aromaticidad y la estructura de la ftaalocianina.
La ruptura reversible de la aromaticidad conduce a cambios significativos y sintonizables en las propiedades fotofísicas.
Este trabajo sienta las bases para el desarrollo de nuevos materiales intercambiables basados en ftaalocianina para aplicaciones avanzadas.

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