Reversible nanocluster structure transformation between face-centered cubic and icosahedral isomers

Structural transformations between isomers of nanoclusters provide a platform to tune their properties and understand the fundamental science due to their intimate structure-property correlation. Herein, we demonstrate a reversible transformation between the face-centered cubic (FCC) and icosahedral isomers of Pt₁Ag₂₈ nanoclusters accomplished in the ligand-exchange processes. Ligand-exchange of 1-adamantanethiolate protected Pt₁Ag₂₈ by cyclohexanethiolate could transform the FCC kernel to the icosahedral isomer. Interestingly, the icosahedral Pt₁Ag₂₈ could be reversibly transformed to the FCC configuration when the cyclohexanethiolate ligand is replaced again by 1-adamantanethiolate. A combination of UV-vis absorption, mass spectrometry, photo-luminescence and X-ray absorption fine structure unambiguously identifies that the FCC-to-icosahedral structure transformation of Pt₁Ag₂₈ involves two distinct stages: (i) ligand-exchange induced outmost motif transformation and (ii) abrupt innermost kernel transformation. As a result of this structural transformation, the emission wavelength of Pt₁Ag₂₈ red-shifts from 672 to 720 nm, and the HOMO-LUMO energy gap reduces from 1.86 to 1.74 eV. This work presents the first example of nanocluster isomers with inter-switching configurations, and will provide new insights into manipulating the properties of nanoclusters through controllably tuning their structures.