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[Ag₄₈(CC ^tBu) ₂₀(CrO₄) ₇: Un nanocúmulo de plata atómicamente preciso protegido por ligandos inorgánicos y orgánicos

Shan-Shan Zhang¹, Fahri Alkan², Hai-Feng Su³

¹Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials , Shandong University , Jinan , 250100 , People's Republic of China.

Journal of the American Chemical Society

|February 20, 2019

Resumen

Los investigadores sintetizaron el primer nanocúmulo de plata (Ag48) cubierto con cromato inorgánico (CrO42-) y ligandos de alquinilo orgánico. Esta nueva estrategia de co-capping ofrece nuevos conocimientos sobre la síntesis de nanocúmulos de plata y las funciones de los ligandos inorgánicos.

Área de la Ciencia:

Ciencia de los nanomateriales
Química inorgánica
Química de las superficies

Sus antecedentes:

La selección de ligandos es crucial para sintetizar nanocúmulos metálicos atómicamente precisos.
Los ligandos orgánicos como los tiolatos y las fosfinas se usan comúnmente, mientras que los ligandos inorgánicos se utilizan insuficientemente.

Objetivo del estudio:

Para sintetizar y caracterizar el primer nanocúmulo de plata (Ag48) cubierto con cromato inorgánico (CrO42-) y ligandos alquiniles orgánicos.
Investigar las funciones del CrO42- inorgánico en la formación y estructura de los nanocúmulos.

Principales métodos:

Síntesis de nanoagrupación de Ag48 mediante el uso de ligandos CrO42- y tBuCC-.
Caracterización estructural mediante difracción de rayos X de un solo cristal.
Análisis de las propiedades electrónicas y coordinación de ligandos.

Principales resultados:

Síntesis exitosa del nanocúmulo Ag48 (SD/Ag48) con una estructura de núcleo y caparazón (núcleo Ag23, caparazón Ag25).
Se observó una coexistencia sin precedentes de ligandos inorgánicos CrO42- y orgánicos tBuCC- en la superficie del nano racimo.
Se identificaron tres funciones clave para CrO42-: pasivar el núcleo, conectar el núcleo y la cáscara y proteger la cáscara.
Se caracteriza SD/Ag48 como un sistema superatómico de 14 electrones con bandas de absorción similares a las moléculas.

Conclusiones:

Estableció una nueva estrategia de ligando inorgánico para la síntesis de nanocúmulos de plata.
Proporcionó nuevos conocimientos sobre la química de coordinación superficial del CrO42- en el control de la forma del nano racimo.
Demostró el potencial de los aniones oxo inorgánicos como ligandos de cierre efectivos para los nanocúmulos metálicos.

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