Details

Autor(en) / Beteiligte

• Li, Yingwei
• Cowan, Michael J
• Zhou, Meng
• Taylor, Michael G
• Wang, He
• Song, Yongbo
• Mpourmpakis, Giannis
• Jin, Rongchao

Titel

Heterometal-Doped M 23 (M = Au/Ag/Cd) Nanoclusters with Large Dipole Moments

Ist Teil von

• ACS nano, 2020-06, Vol.14 (6), p.6599-6606

Ort / Verlag

United States

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Dipole moment (μ) is a critical parameter for molecules and nanomaterials as it affects many properties. In metal-thiolate (SR) nanoclusters (NCs), μ is commonly low (0-5 D) compared to quantum dots. Herein, we report a doping strategy to give giant dipoles (∼18 D) in M (M = Au/Ag/Cd) NCs, falling in the experimental trend for II-VI quantum dots. In M NCs, high μ is caused by the Cd-Br bond and the arrangement of heteroatoms along the axis. Strong dipole-dipole interactions are observed in crystalline state, with energy exceeding 5 kJ/mol, directing a "head-to-tail" alignment of Au Ag Cd (SR) X (SR = adamantanethiolate) dipoles. The alignment can be controlled by doping. The optical absorption peaks of M show solvent polarity-dependent shifts (∼25 meV) with negative solvatochromism. Detailed electronic structures of M are revealed by density functional theory and time-dependent DFT calculations. Overall, the doping strategy for obtaining large dipole moments demonstrates an atomic-level design of clusters with useful properties.