Highly modulated supported triazolium-based ionic liquids: direct control of the electronic environment on Cu nanoparticles

Valdebenito, Cristi�n; Pinto, Jose; Nazarkovsky, Michael; Chac�n, Gustavo; Mart�nez-Ferrat�, Oriol; Wrighton-Araneda, Kerry; Cort�s-Arriagada, Diego; Camarada, Mar�a Bel�n; Alves Fernandes, Jesum; Abarca, Gabriel

Abstract

A series of new triazolium-based supported ionic liquids (SILPs), decorated with Cu NPs, were successfully prepared and applied to the N-arylation of aryl halides with anilines. The triazoles moieties were functionalised using copper-catalysed azide–alkyne cycloaddition. SILP surface characterisation showed a strong correlation between the triazolium cation volume and textural properties. STEM images showed well-dispersed Cu NPs on SILPs with a mean diameter varying from 3.6 to 4.6 nm depending on the triazolium cation used. Besides, XPS results suggest that the Cu(0)/Cu(I) ratio can be modulated by the electronic density of triazolium substituents. XPS and computational analysis gave mechanistic insights into the Cu NP stabilisation pathways, where the presence of electron-rich groups attached to a triazolium ring plays a critical role in leading to a cation adsorption pathway (Eads = 72 kcal mol−1). In contrast, less electron-rich groups favour the anion adsorption pathway (Eads = 63 kcal mol−1). The Cu@SILP composite with electron-rich groups showed the highest activity for the C–N Ullmann coupling reaction, which suggests that electron-rich groups might act as an electron-like reservoir to facilitate oxidative addition for N-arylation. This strategy firmly suggests the strong dependence of the nature of triazolium-based SILPs on the Cu NP surface active sites, which may provide a new environment to confine and stabilise MNPs for catalytic applications.

Citation

Valdebenito, C., Pinto, J., Nazarkovsky, M., Chacón, G., Martínez-Ferraté, O., Wrighton-Araneda, K., …Abarca, G. (2020). Highly modulated supported triazolium-based ionic liquids: direct control of the electronic environment on Cu nanoparticles. Nanoscale Advances, 2(3), 1325-1332. https://doi.org/10.1039/d0na00055h

• Journal Article Type: Article
• Acceptance Date: Feb 9, 2020
• Online Publication Date: Feb 12, 2020
• Publication Date: Mar 1, 2020
• Deposit Date: Jul 31, 2020
• Publicly Available Date: Aug 3, 2020
• Journal: Nanoscale Advances
• Print ISSN: 2516-0230
• Electronic ISSN: 2516-0230
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 2
• Issue: 3
• Pages: 1325-1332
• DOI: https://doi.org/10.1039/d0na00055h
• Public URL: https://nottingham-repository.worktribe.com/output/4738211
• Publisher URL: https://pubs.rsc.org/en/content/articlelanding/2020/NA/D0NA00055H#!divAbstract
• Additional Information: : This document is Similarity Check deposited; CrossRef DOI Link to Correction:: https://doi.org/10.1039/D0NA90022B; : Supplementary Information; : Gustavo Chacón (ORCID); : Oriol Martínez-Ferraté (ORCID); : Oriol Martínez-Ferraté (ResearcherID); : Diego Cortés-Arriagada (ORCID); : María Belén Camarada (ORCID); : Jesum Alves Fernandes (ORCID); : Jesum Alves Fernandes (ResearcherID); : Gabriel Abarca (ORCID); : Gabriel Abarca (ResearcherID); : Single-blind; : Received 20 January 2020; Accepted 9 February 2020; Accepted Manuscript published 12 February 2020; Advance Article published 2 March 2020; Version of Record published 17 March 2020