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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.