title: Tailoring the Electronic and Catalytic Properties of Au25 Nanoclusters via Ligand Engineering.
abstract: To explore the electronic and catalytic properties of nanoclusters, here we report an aromatic-thiolate-protected gold nanocluster, [Au25(SNap)18](-) [TOA](+), where SNap = 1-naphthalenethiolate and TOA = tetraoctylammonium. It exhibits distinct differences in electronic and catalytic properties in comparison with the previously reported [Au25(SCH2CH2Ph)18](-), albeit their skeletons (i.e., Au25S18 framework) are similar. A red shift by ∼10 nm in the HOMO-LUMO electronic absorption peak wavelength is observed for the aromatic-thiolate-protected nanocluster, which is attributed to its dilated Au13 kernel. The unsupported [Au25(SNap)18](-) nanoclusters show high thermal and antioxidation stabilities (e.g., at 80 °C in the present of O2, excess H2O2, or TBHP) due to the effects of aromatic ligands on stabilization of the nanocluster's frontier orbitals (HOMO and LUMO). Furthermore, the catalytic activity of the supported Au25(SR)18/CeO2 (R = Nap, Ph, CH2CH2Ph, and n-C6H13) is examined in the Ullmann heterocoupling reaction between 4-methyl-iodobenzene and 4-nitro-iodobenzene. Results show that the activity and selectivity of the catalysts are largely influenced by the chemical nature of the protecting thiolate ligands. This study highlights that the aromatic ligands not only lead to a higher conversion in catalytic reaction but also markedly increase the yield of the heterocoupling product (4-methyl-4'-nitro-1,1'-biphenyl). Through a combined approach of experiment and theory, this study sheds light on the structure-activity relationships of the Au25 nanoclusters and also offers guidelines for tailoring nanocluster properties by ligand engineering for specific applications.
authors.affiliation: Gold Catalysis Research Centre, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Gao
authors.initials: G
authors.lastname: Li
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Hadi
authors.initials: H
authors.lastname: Abroshan
authors.affiliation: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Chong
authors.initials: C
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Shuo
authors.initials: S
authors.lastname: Zhuo
authors.affiliation: Gold Catalysis Research Centre, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Zhimin
authors.initials: Z
authors.lastname: Li
authors.affiliation: Gold Catalysis Research Centre, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Xie
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.|School of Computational Sciences, Korea Institute for Advanced Study , Seoul 02455, Korea.
authors.forename: Hyung J
authors.initials: HJ
authors.lastname: Kim
authors.affiliation: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Nathaniel L
authors.initials: NL
authors.lastname: Rosi
authors.affiliation: Department of Chemistry, Carnegie Mellon University , Pittsburgh, Pennsylvania 15213, United States.
authors.forename: Rongchao
authors.initials: R
authors.lastname: Jin
mesh_terms: D002384:Catalysis; D006046:Gold; D006861:Hydrogen Peroxide; D008024:Ligands; D053758:Nanoparticles
chemical_list: D008024:Ligands; D006046:Gold; D006861:Hydrogen Peroxide
keywords: Au25; Ullmann coupling; gold; ligand effects; nanoclusters