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Interconversión entre las configuraciones superatómicas de 6 y 8 electrones de los cúmulos M@Au24 ((SR) 18) (M = Pd,

Kyuju Kwak¹, Qing Tang², Minseok Kim¹

¹Department of Chemistry, Yonsei University , Seoul 120-749, Korea.

Journal of the American Chemical Society

|July 30, 2015

Resumen

Los racimos de oro protegidos por tiolato dopados con paladio o platino exhiben una configuración estable de 6 electrones, a diferencia de la configuración de 8 electrones de los racimos de oro puro. Este dopaje reduce significativamente el espacio orbital molecular ocupado más alto y el orbital molecular desocupado más bajo, alterando la estructura electrónica.

Área de la Ciencia:

Química de los nanomateriales
Química de los racimos superatómicos
Química computacional

Sus antecedentes:

Los racimos de oro protegidos por tiolato, específicamente [Au25 ((SR)) 18 ((-), logran una estabilidad excepcional debido a las capas de electrones superatómicos cerrados (configuración de 8 electrones).
Comprender la estructura electrónica y la estabilidad de los grupos metálicos es crucial para el desarrollo de nuevos nanomateriales funcionales.

Objetivo del estudio:

Investigar el efecto de la sustitución del átomo de oro del núcleo en [Au25 ((SR) 18) ((-) por el paladio (Pd) o el platino (Pt).
Para caracterizar la estructura electrónica, la estabilidad y las propiedades geométricas de los grupos resultantes [MAu24 ((SR) 18) ((M = Pd, Pt)).
Para explorar la interconversión entre diferentes configuraciones de electrones superatómicos en estos grupos dopados.

Principales métodos:

Síntesis y caracterización de los racimos de oro dopados con paladio y platino protegidos con tiolato ([PdAu24(SR) 18) ((0) y [PtAu24(SR) 18) ((0)).
Estudios voltamétricos para determinar las brechas entre el orbital molecular ocupado más alto y el orbital molecular desocupado más bajo (HOMO-LUMO).
Investigaciones de la teoría funcional de la densidad (DFT) para confirmar estructuras electrónicas y analizar optimizaciones geométricas.

Principales resultados:

Se sintetizaron cúmulos estables [MAu24(SR) 18) (M = Pd, Pt), que exhiben una configuración de 6 electrones superatómica.
Los cálculos de voltametría y DFT revelaron una reducción significativa de las brechas HOMO-LUMO (0,29 0,33 eV) en comparación con [Au25 SR] 18 - (1,35 eV).
Se observó una distorsión similar a Jahn-Teller del núcleo MAu12 en los cúmulos de 6 electrones, lo que llevó a la división de los orbitales 1P.
Estos cúmulos dopados demostraron una carga electrónica reversible para formar cúmulos de 8 electrones [MAu24 ((SR) 18 ((2-).

Conclusiones:

El reemplazo del átomo de oro central por Pd o Pt en racimos Au25 conduce a configuraciones superatómicas estables de 6 electrones con propiedades electrónicas significativamente alteradas.
La disminución observada en las brechas HOMO-LUMO se atribuye a las distorsiones de Jahn-Teller en los cúmulos dopados de 6 electrones.
La interconversión reversible entre las configuraciones de 6 y 8 electrones es posible en estos nuevos grupos de oro dopados.

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