Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Olga Guselnikova, Jiří Váňa, Linh Trinh Phuong, Illia Panov, Lubomír Rulíšek, Andrii Trelin, Pavel Postnikov, Václav Švorčík, Erik Andris, Oleksiy Lyutakov

Research output: Contribution to journalArticlepeer-review

Abstract

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide-alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to −35 °C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at −35 °C.

Original languageEnglish
Pages (from-to)5591-5598
Number of pages8
JournalChemical Science
Volume12
Issue number15
DOIs
Publication statusPublished - 21 Apr 2021

ASJC Scopus subject areas

  • Chemistry(all)

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