TY - JOUR
T1 - Can Plasmon Change Reaction Path? Decomposition of Unsymmetrical Iodonium Salts as an Organic Probe
AU - Miliutina, Elena
AU - Guselnikova, Olga
AU - Soldatova, Natalia S.
AU - Bainova, Polina
AU - Elashnikov, Roman
AU - Fitl, Přemysl
AU - Kurten, Theo
AU - Yusubov, Mekhman S.
AU - Švorčík, Václav
AU - Valiev, Rashid R.
AU - Chehimi, Mohamed M.
AU - Lyutakov, Oleksiy
AU - Postnikov, Pavel S.
PY - 2020/7/16
Y1 - 2020/7/16
N2 - Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. However, the mechanistic insights of interaction between plasmon energy and organic molecules is still under debate. Herein, we proposed a comprehensive study of the plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an organic probe. The experimental and theoretical analysis allow us to exclude the possible thermal effect or hot electron transfer. We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C-I bond with the formation of electron-rich radical species, which cannot be explained by the hot electron excitation or thermal effects. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of a dissociative excited state according to quantum-chemical modeling, which provides novel opportunities for the fine control of reactivity using plasmon energy.
AB - Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. However, the mechanistic insights of interaction between plasmon energy and organic molecules is still under debate. Herein, we proposed a comprehensive study of the plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an organic probe. The experimental and theoretical analysis allow us to exclude the possible thermal effect or hot electron transfer. We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C-I bond with the formation of electron-rich radical species, which cannot be explained by the hot electron excitation or thermal effects. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of a dissociative excited state according to quantum-chemical modeling, which provides novel opportunities for the fine control of reactivity using plasmon energy.
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U2 - 10.1021/acs.jpclett.0c01350
DO - 10.1021/acs.jpclett.0c01350
M3 - Article
C2 - 32603124
AN - SCOPUS:85088268696
VL - 11
SP - 5770
EP - 5776
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 14
ER -