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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-PPh3)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(d15-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.
