Viraj Dhanushka Thanthirige

Ultrabright Luminescence from Gold Nanoclusters: Rigidifying the Au(I)–Thiolate Shell

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.

Au21S(SAdm)15: An Anisotropic Gold Nanomolecule. Optical and Photoluminescence Spectroscopy and First-Principles Theoretical Analysis

We introduce a class of gold nanomolecules exhibiting anisotropy as a major feature by reporting steady-state and time-resolved photoluminescence and anisotropy measurements and in-depth theoretical analysis of energetics and optical response of a recently synthesized Au21S(SAdm)15 nanomolecule (SAdm = adamantanethiol). Starting from single-crystal X-ray data showing that Au21S(SAdm)15 exhibits a symmetry-broken structure, we unambiguously demonstrate how this translates into a striking anisotropy of its properties, for example, of its (chiro)optical absorption spectrum of great promise for sensing, optoelectronic, and electrochemical applications, and argue about the abundance and general significance of this class of compounds.

Energy Gap Law for Exciton Dynamics in Gold Cluster Molecules

The energy gap law relates the nonradiative decay rate to the energy gap separating the ground and excited states. Here we report that the energy gap law can be applied to exciton dynamics in gold cluster molecules. Size-dependent electrochemical and optical properties were investigated for a series of n-hexanethiolate-protected gold clusters ranging from Au25 to Au333. Voltammetric studies reveal that the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps of these clusters decrease with increasing cluster size. Combined femtosecond and nanosecond time-resolved transient absorption measurements show that the exciton lifetimes decrease with increasing cluster size. Comparison of the size-dependent exciton lifetimes with the HOMO-LUMO gaps shows that they are linearly correlated, demonstrating the energy gap law for excitons in these gold cluster molecules.