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 Pt(1)Ag(28) nanoclusters accomplished in the ligand-exchange processes. Ligand-exchange of 1-adamantanethiolate protected Pt(1)Ag(28) by cyclohexanethiolate could transform the FCC kernel to the icosahedral isomer. Interestingly, the icosahedral Pt(1)Ag(28) 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 Pt(1)Ag(28) 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 Pt(1)Ag(28) 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.