NMR characterization of ligand binding and exchange dynamics in triphenylphosphine-capped gold nanoparticles

Ramesh Sharma, Gregory P. Holland, Virgil C. Solomon, Herbert Zimmermann, Steven Schiffenhaus, Samrat A. Amin, Daniel Buttry, Jeffery Yarger

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Abstract

Triphenylphosphine (PPh3)-capped 1.8 nm diameter gold nanoparticles (AuNPs) are characterized by a combination of 1H, 2H, and 31P solution-and solid-state NMR. The 31P{1H} NMR resonance associated with the surface-bound PPh3 is clearly identified and is present as a broad peak centered at 56 ppm. 31P and 1H hole burning NMR experiments show that the line broadening associated with the surface-bound PPh3 is primarily due to a variety of different chemical shift environments at the surface of the nanoparticles. The surface bound PPh3 can be displaced with either d15-PPh3 or Au(d15-PPh 3)Cl in CD2Cl2 solution. In both cases, exchange results in loss of Au(PPh3)Cl from the nanoparticle surface, with no evidence for loss of the PPh3 ligand alone. Solution-state NMR was used to determine the room temperature rate constants for these exchange processes, with values of 0.17 and 0.20 min-1, respectively. Thus, essentially the same rate is observed for displacement of Au(PPh3)Cl from the surface with either d15-PPh3 or Au(d 15-PPh3)Cl. The observed 31P chemical shift of surface-bound PPh3 is consistent with mixed valence Au(0) and Au(I) at the nanoparticle surfaces, suggesting the presence of surface-bound Au complexes.

Original languageEnglish (US)
Pages (from-to)16387-16393
Number of pages7
JournalJournal of Physical Chemistry C
Volume113
Issue number37
DOIs
StatePublished - Sep 17 2009

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Gold
Ligands
Nuclear magnetic resonance
gold
Nanoparticles
nanoparticles
nuclear magnetic resonance
ligands
Chemical shift
chemical equilibrium
triphenylphosphine
hole burning
Rate constants
Ion exchange
solid state
valence
room temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

NMR characterization of ligand binding and exchange dynamics in triphenylphosphine-capped gold nanoparticles. / Sharma, Ramesh; Holland, Gregory P.; Solomon, Virgil C.; Zimmermann, Herbert; Schiffenhaus, Steven; Amin, Samrat A.; Buttry, Daniel; Yarger, Jeffery.

In: Journal of Physical Chemistry C, Vol. 113, No. 37, 17.09.2009, p. 16387-16393.

Research output: Contribution to journalArticle

Sharma R, Holland GP, Solomon VC, Zimmermann H, Schiffenhaus S, Amin SA et al. NMR characterization of ligand binding and exchange dynamics in triphenylphosphine-capped gold nanoparticles. Journal of Physical Chemistry C. 2009 Sep 17;113(37):16387-16393. https://doi.org/10.1021/jp905141h
Sharma, Ramesh ; Holland, Gregory P. ; Solomon, Virgil C. ; Zimmermann, Herbert ; Schiffenhaus, Steven ; Amin, Samrat A. ; Buttry, Daniel ; Yarger, Jeffery. / NMR characterization of ligand binding and exchange dynamics in triphenylphosphine-capped gold nanoparticles. In: Journal of Physical Chemistry C. 2009 ; Vol. 113, No. 37. pp. 16387-16393.
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