title: Quantified Binding Scale of Competing Ligands at the Surface of Gold Nanoparticles: The Role of Entropy and Intermolecular Forces.
abstract: A basic understanding of the driving forces for the formation of multiligand coronas or self-assembled monolayers over metal nanoparticles is mandatory to control and predict the properties of ligand-protected nanoparticles. Herein,1H nuclear magnetic resonance experiments and advanced density functional theory (DFT) modeling are combined to highlight the key parameters defining the efficiency of ligand exchange on dispersed gold nanoparticles. The compositions of the surface and of the liquid reaction medium are quantitatively correlated for bifunctional gold nanoparticles protected by a range of competing thiols, including an alkylthiol, arylthiols of varying chain length, thiols functionalized by ethyleneglycol units, and amide groups. These partitions are used to build scales that quantify the ability of a ligand to exchange dodecanethiol. Such scales can be used to target a specific surface composition by choosing the right exchange conditions (ligand ratio, concentrations, and particle size). In the specific case of arylthiols, the exchange ability scale is exploited with the help of DFT modeling to unveil the roles of intermolecular forces and entropic effects in driving ligand exchange. It is finally suggested that similar considerations may apply to other ligands and to direct biligand synthesis.
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: Claire
authors.initials: C
authors.lastname: Goldmann
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: François
authors.initials: F
authors.lastname: Ribot
authors.affiliation: Preline, Facultad de Ingeniería Química, Universidad Nacional del Litoral, 3000, Santa Fe, Argentina.
authors.forename: Leonardo F
authors.initials: LF
authors.lastname: Peiretti
authors.affiliation: Preline, Facultad de Ingeniería Química, Universidad Nacional del Litoral, 3000, Santa Fe, Argentina.
authors.forename: Paola
authors.initials: P
authors.lastname: Quaino
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: Frederik
authors.initials: F
authors.lastname: Tielens
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: Clément
authors.initials: C
authors.lastname: Sanchez
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: Corinne
authors.initials: C
authors.lastname: Chanéac
authors.affiliation: Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), Sorbonne, Universités-UPMC Univ Paris 06, CNRS, Collège de France, 4 Place Jussieu, 75005, Paris, France.
authors.forename: David
authors.initials: D
authors.lastname: Portehault
keywords: density functional theory; gold nanoparticles; ligand exchange; multifunctional nanoparticles; nuclear magnetic resonance