Autor según el artículo: Hu, Yajing; Yao, Yang-Rong; Liu, Xuechen; Yu, Ao; Xie, Xiaoming; Abella, Laura; Rodriguez-Fortea, Antonio; Poblet, Josep M.; Akasaka, Takeshi; Peng, Ping; Zhang, Qianyan; Xie, Su-Yuan; Li, Fang-Fang; Lu, Xing;

Departamento: Química Física i Inorgànica

Autor/es de la URV: Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio

Palabras clave: Isomers I-h-sc3n-at-c-80 Endohedral metallofullerenes Electrosynthesis Efficient Acid

Resumen: An attempt to achieve heterocyclic cycloadducts of Sc3N@I-h-C-80 via reaction with Ph2C=O, PhC equivalent to CPh or PhC equivalent to N in the presence of tetrabutylammonium hydroxide (TBAOH) stored in CH3OH led to the formation of the unexpected bismethoxyl adducts of Sc3N@I-h-C-80 (1 and 2). Further studies reveal that TBAOH in CH3OH can boost the CH3O- addition efficiently, regardless of the presence of other reagents. Single-crystal X-ray diffraction results firmly assign the molecular structures of 1 and 2 as respective 1,4- and 1,2-bismethoxyl adducts, and reveal unusual relationships between the internal Sc3N cluster and the addition modes, in addition to the unusual packing mode in view of the orientation of the methoxyl groups. Electrochemical results demonstrate smaller electrochemical gaps for 1 and 2, relative to that of Sc3N@I-h-C-80, confirming their better electroactive properties. Finally, a plausible reaction mechanism involving anion addition and a radical reaction was proposed, presenting new insights into the highly selective reactions between the methoxyl anion and metallofullerenes. 1 and 2 represent the first examples of methoxyl derivatives of metallofullerenes. This work not only presents a novel and facile strategy for the controllable synthesis of alkoxylated metallofullerene derivatives, but also provides new non-cycloadducts for the potential applications of EMFs.

Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

Direcció de correo del autor: antonio.rodriguezf@urv.cat josepmaria.poblet@urv.cat

Identificador del autor: 0000-0001-5884-5629 0000-0002-4533-0623

Fecha de alta del registro: 2023-02-19

Volumen de revista: 12

Versión del articulo depositado: info:eu-repo/semantics/publishedVersion

Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2021/SC/D1SC01178B#!divAbstract

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Chemical Science. 12 (23): 8123-8130

Referencia de l'ítem segons les normes APA: Hu, Yajing; Yao, Yang-Rong; Liu, Xuechen; Yu, Ao; Xie, Xiaoming; Abella, Laura; Rodriguez-Fortea, Antonio; Poblet, Josep M.; Akasaka, Takeshi; Peng, P (2021). Unexpected formation of 1,2-and 1,4-bismethoxyl Sc3N@I-h-C-80 derivatives via regioselective anion addition: an unambiguous structural identification and mechanism study. Chemical Science, 12(23), 8123-8130. DOI: 10.1039/d1sc01178b

DOI del artículo: 10.1039/d1sc01178b

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2021

Tipo de publicación: Journal Publications