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.

Department of Solid State Engineering University of Chemistry and Technology 166 28 Prague Czech Republic

Group of Advanced Materials and Organic Synthesis Institute of Chemical Process Fundamentals Czech Academy of Sciences Rozvojová 1 135 165 02 Prague Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo náměstí 2 166 10 Prague 6 Czech Republic

Institute of Organic Chemistry and Technology Faculty of Chemical Technology University of Pardubice Studentská 573 532 10 Pardubice Czech Republic

Research School of Chemistry and Applied Biomedical Sciences National Research Tomsk Polytechnic University Lenin Avenue 30 Tomsk 634050 Russia

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