TY - JOUR
T1 - Ligand Control over the Electronic Properties within the Metallic Core of Gold Nanoparticles
AU - Cirri, Anthony
AU - Silakov, Alexey
AU - Lear, Benjamin J.
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/9/1
Y1 - 2015/9/1
N2 - The behavior of electrons within the metallic core of gold nanoparticles (AuNPs) can be controlled by the nature of the surface chemistry of the AuNPs. Specifically, the conduction electron spin resonance (CESR) spectra of AuNPs of diameter 1.8-1.9nm are sensitive to ligand exchange of hexanethiol for 4-bromothiophenol on the surface of the nanoparticle. Chemisorption of the aromatic ligand leads to a shift in the metallic electron's g-factor toward the value expected for pure gold systems, suggesting an increase in metallic character for the electrons within the gold core. Analysis by UV/Vis absorption spectroscopy reveals a concomitant bathochromic shift of the surface plasmon resonance band of the AuNP, indicating that other electronic properties of AuNPs are also affected by the ligand exchange. In total, our results demonstrate that the chemical nature of the ligand controls the valence band structure of AuNPs. Good as gold: The surface chemistry of gold nanoparticles (AuNPs) is shown to influence the behavior of electrons within the metallic core. Conduction electron spin resonance (CESR) spectra and surface plasmon resonance bands for AuNPs are sensitive to ligand exchange of hexanethiol for 4-bromothiophenol on the surface of the NPs, demonstrating that the chemical nature of the ligand controls the valence band structure of AuNPs.
AB - The behavior of electrons within the metallic core of gold nanoparticles (AuNPs) can be controlled by the nature of the surface chemistry of the AuNPs. Specifically, the conduction electron spin resonance (CESR) spectra of AuNPs of diameter 1.8-1.9nm are sensitive to ligand exchange of hexanethiol for 4-bromothiophenol on the surface of the nanoparticle. Chemisorption of the aromatic ligand leads to a shift in the metallic electron's g-factor toward the value expected for pure gold systems, suggesting an increase in metallic character for the electrons within the gold core. Analysis by UV/Vis absorption spectroscopy reveals a concomitant bathochromic shift of the surface plasmon resonance band of the AuNP, indicating that other electronic properties of AuNPs are also affected by the ligand exchange. In total, our results demonstrate that the chemical nature of the ligand controls the valence band structure of AuNPs. Good as gold: The surface chemistry of gold nanoparticles (AuNPs) is shown to influence the behavior of electrons within the metallic core. Conduction electron spin resonance (CESR) spectra and surface plasmon resonance bands for AuNPs are sensitive to ligand exchange of hexanethiol for 4-bromothiophenol on the surface of the NPs, demonstrating that the chemical nature of the ligand controls the valence band structure of AuNPs.
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U2 - 10.1002/anie.201505933
DO - 10.1002/anie.201505933
M3 - Article
AN - SCOPUS:84942292652
SN - 1433-7851
VL - 54
SP - 11750
EP - 11753
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 40
ER -