4.8 Article

Nanoparticle-mediated intervalence transfer

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 130, Issue 36, Pages 12156-12162

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja803887b

Keywords

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Funding

  1. National Science Foundation [CHE-0456130, CHE-0718190, CHE-0348956]
  2. Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]

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Nanoparticle-mediated intervalence transfer was reported with ferrocene moieties that were attached onto the ruthenium nanoparticle surface by ruthenium-carbene pi bonds. The resulting particles exhibited two pairs of voltammetric waves with a potential spacing of about 200 mV and a rather intense absorption peak in the near-infrared range (similar to 1930 nm) at mixed valence. Both features suggested Class II characteristics of the intraparticle intervalence transfer that mainly arose from through-bond interactions between the metal centers. Quantum calculations based on density functional theory showed that the nanoparticle core electrons served as conducting band states for the effective charge delocalization between particle-bound ferrocene moieties.

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