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Hot Electrons Generated in Chiral Plasmonic Nanocrystals as a Mechanism for Surface Photochemistry and Chiral Growth.
Khorashad, Larousse Khosravi; Besteiro, Lucas V; Correa-Duarte, Miguel A; Burger, Sven; Wang, Zhiming M; Govorov, Alexander O.
Afiliação
  • Khorashad LK; Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China.
  • Besteiro LV; Department of Physics and Astronomy, Ohio University, Athens, Ohio 45701, United States.
  • Correa-Duarte MA; Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China.
  • Burger S; Centre Énergie Matériaux et Télécommunications, Institut National de la Recherche Scientifique, 1650 Boul. Lionel Boulet, Varennes, QC J3X 1S2, Canada.
  • Wang ZM; Department of Physical Chemistry, Center for Biomedical Research (CINBIO), Southern Galicia Institute of Health Research (IISGS), and Biomedical Research, Networking Center for Mental Health (CIBERSAM), Universidade de Vigo, 36310 Vigo, Spain.
  • Govorov AO; Zuse Institute Berlin, Takustrasse 7, 14195 Berlin, Germany.
J Am Chem Soc ; 142(9): 4193-4205, 2020 03 04.
Article em En | MEDLINE | ID: mdl-32026688
ABSTRACT
The realization of chiral photochemical reactions at the molecular level has proven to be a challenging task, with invariably low efficiencies originating from very small optical circular dichroism signals. On the contrary, colloidal nanocrystals offer a very large differential response to circularly polarized light when designed with chiral geometries. We propose taking advantage of this capability, introducing a novel mechanism driving surface photochemistry in a chiral nanocrystal. Plasmonic nanocrystals exhibit anomalously large asymmetry factors in optical circular dichroism (CD), and the related hot-electron generation shows in turn a very strong asymmetry, serving as a mechanism for chiral growth. Through theoretical modeling, we show that chiral plasmonic nanocrystals can enable chiral surface growth based on the generation of energetic (hot) electrons. Using simple and realistic phenomenological models, we illustrate how this kind of surface photochemistry can be observed experimentally. The proposed mechanism is efficient if it operates on an already strongly chiral nanocrystal, whereas our proposed mechanism does not show chiral growth for initially nonchiral structures in a solution. The asymmetry factors for the chiral effects, driven by hot electrons, exceed the values observed in chiral molecular photophysics at least 10-fold. The proposed chiral-growth mechanism for the transformation of plasmonic colloids is fundamentally different to the traditional schemes of chiral photochemistry at the molecular level.

Texto completo: 1 Base de dados: MEDLINE Tipo de estudo: Prognostic_studies / Qualitative_research Idioma: En Ano de publicação: 2020 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Tipo de estudo: Prognostic_studies / Qualitative_research Idioma: En Ano de publicação: 2020 Tipo de documento: Article