Author, as appears in the article.: 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
Department: Química Física i Inorgànica
URV's Author/s: Abella Guzman, Laura / Poblet Rius, Josep Maria / Rodríguez Fortea, Antonio
Keywords: Isomers I-h-sc3n-at-c-80 Endohedral metallofullerenes Electrosynthesis Efficient Acid
Abstract: 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.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: josepmaria.poblet@urv.cat antonio.rodriguezf@urv.cat
Author identifier: 0000-0002-4533-0623 0000-0001-5884-5629
Record's date: 2024-10-12
Journal volume: 12
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2021/SC/D1SC01178B#!divAbstract
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Chemical Science. 12 (23): 8123-8130
APA: Hu, Yajing; Yao, Yang-Rong; Liu, Xuechen; Yu, Ao; Xie, Xiaoming; Abella, Laura; Rodriguez-Fortea, Antonio; Poblet, Josep M; Akasaka, Takeshi; Peng, Pi (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
Article's DOI: 10.1039/d1sc01178b
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications