title: Ultrabright Luminescence from Gold Nanoclusters: Rigidifying the Au(I)-Thiolate Shell.
abstract: Luminescent nanomaterials have captured the imagination of scientists for a long time and offer great promise for applications in organic/inorganic light-emitting displays, optoelectronics, optical sensors, biomedical imaging, and diagnostics. Atomically precise gold clusters with well-defined core-shell structures present bright prospects to achieve high photoluminescence efficiencies. In this study, gold clusters with a luminescence quantum yield greater than 60% were synthesized based on the Au22(SG)18 cluster, where SG is glutathione, by rigidifying its gold shell with tetraoctylammonium (TOA) cations. Time-resolved and temperature-dependent optical measurements on Au22(SG)18 have shown the presence of high quantum yield visible luminescence below freezing, indicating that shell rigidity enhances the luminescence quantum efficiency. To achieve high rigidity of the gold shell, Au22(SG)18 was bound to bulky TOA that resulted in greater than 60% quantum yield luminescence at room temperature. Optical measurements have confirmed that the rigidity of gold shell was responsible for the luminescence enhancement. This work presents an effective strategy to enhance the photoluminescence efficiencies of gold clusters by rigidifying the Au(I)-thiolate shell.
authors.affiliation: †Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
authors.forename: Kyunglim
authors.initials: K
authors.lastname: Pyo
authors.affiliation: ‡Department of Chemistry, Western Michigan University, Kalamazoo Michigan 49008, United States.
authors.forename: Viraj Dhanushka
authors.initials: VD
authors.lastname: Thanthirige
authors.affiliation: †Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
authors.forename: Kyuju
authors.initials: K
authors.lastname: Kwak
authors.affiliation: †Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
authors.forename: Prabhu
authors.initials: P
authors.lastname: Pandurangan
authors.affiliation: ‡Department of Chemistry, Western Michigan University, Kalamazoo Michigan 49008, United States.
authors.forename: Guda
authors.initials: G
authors.lastname: Ramakrishna
authors.affiliation: †Department of Chemistry, Yonsei University, Seoul 120-749, Korea.
authors.forename: Dongil
authors.initials: D
authors.lastname: Lee
mesh_terms: D002412:Cations / Q000737:chemistry; D005978:Glutathione / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D049449:Luminescence; D049408:Luminescent Agents / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D008958:Models, Molecular; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D002412:Cations; D049408:Luminescent Agents; D000644:Quaternary Ammonium Compounds; D013438:Sulfhydryl Compounds; D006046:Gold; D005978:Glutathione