Heterometal-Doped M23 (M = Au/Ag/Cd) Nanoclusters with Large Dipole Moments

Dipole moment (mu) is a critical parameter for molecules and nanomaterials as it affects many properties. In metal-thiolate (SR) nanoclusters (NCs), pi is commonly low (0-5 D) compared to quantum dots. Herein, we report a doping strategy to give giant dipoles (similar to 18 D) in M-23 (M = Au/Ag/Cd) NCs, falling in the experimental trend for II-VI quantum dots. In M-23 NCs, high it is caused by the Cd-Br bond and the arrangement of heteroatoms along the C-3 axis. Strong dipole-dipole interactions are observed in crystalline state, with energy exceeding 5 kJ/mol, directing a head-to-tail alignment of Au22-nAgnCd1(SR)(15)X (SR = adamantanethiolate) dipoles. The alignment can be controlled by mu via doping. The optical absorption peaks of M-23 show solvent polarity-dependent shifts (similar to 25 meV) with negative solvatochromism. Detailed electronic structures of M-23 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.