Establishing plasmon contribution to chemical reactions: alkoxyamines as a thermal probe

Establishing plasmon contribution to chemical reactions: alkoxyamines as a thermal probe Full article

Journal

Chemical Science
ISSN: 2041-6520 , E-ISSN: 2041-6539

Output data

Year: 2021, Volume: 12, Number: 11, Pages: 4154-4161 Pages count : 8 DOI: 10.1039/d0sc06470j

Authors

Guselnikova Olga ¹ , Audran Gérard ² , Joly Jean-Patrick ² , Trelin Andrii ³ , Tretyakov Evgeny V. ⁴ , Svorcik Vaclav ³ , Lyutakov Oleksiy ³ , Marque Sylvain R.A. ² , Postnikov Pavel ^1,3

Affiliations

1	Research School of Chemistry and Applied Biomedical Sciences, Tomsk Polytechnic University, Russian Federation
2	Aix-Marseille Univ, CNRS, ICR case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
3	Department of Solid-State Engineering, University of Chemistry and Technology, Prague, Czech Republic
4	N.D. Zelinsky Institute of Organic Chemistry, Leninsky Prospect, 47, Moscow 119991, Russia

The nature of plasmon interaction with organic molecules is a subject of fierce discussion about thermal and non-thermal effects. Despite the abundance of physical methods for evaluating the plasmonic effects, chemical insight has not been reported yet. In this contribution, we propose a chemical insight into the plasmon effect on reaction kinetics using alkoxyamines as an organic probe through their homolysis, leading to the generation of nitroxide radicals. Alkoxyamines (TEMPO- and SG1-substituted) with well-studied homolysis behavior are covalently attached to spherical Au nanoparticles. We evaluate the kinetic parameters of homolysis of alkoxyamines attached on a plasmon-active surface under heating and irradiation at a wavelength of plasmon resonance. The estimation of kinetic parameters from experiments with different probes (Au–TEMPO, Au–SG1, Au–SG1–TEMPO) allows revealing the apparent differences associated with the non-thermal contribution of plasmon activation. Moreover, our findings underline the dependency of kinetic parameters on the structure of organic molecules, which highlights the necessity to consider the nature of organic transformations and molecular structure in plasmon catalysis.

Guselnikova O. , Audran G. , Joly J-P. , Trelin A. , Tretyakov E.V. , Svorcik V. , Lyutakov O. , Marque S.R.A. , Postnikov P.
Establishing plasmon contribution to chemical reactions: alkoxyamines as a thermal probe
Chemical Science. 2021. V.12. N11. P.4154-4161. DOI: 10.1039/d0sc06470j WOS Scopus OpenAlex

Web of science:	WOS:000632580200034
Scopus:	2-s2.0-85103356049
OpenAlex:	W3122903940

DB	Citing
OpenAlex	20
Scopus	12
Web of science	16