Thermally-induced reversible structural isomerization in colloidal semiconductor CdS magic-size clusters

Abstract

Structural isomerism of colloidal semiconductor nanocrystals has been largely unexplored. Here, we report one pair of structural isomers identified for colloidal nanocrystals which exhibit thermally-induced reversible transformations behaving like molecular isomerization. The two isomers are CdS magic-size clusters with sharp absorption peaks at 311 and 322 nm. They have identical cluster masses, but slightly different structures. Furthermore, their interconversions follow first-order unimolecular reaction kinetics. We anticipate that such isomeric kinetics are applicable to a variety of small-size functional nanomaterials, and that the methodology developed for our kinetic study will be helpful to investigate and exploit solid–solid transformations in other semiconductor nanocrystals. The findings on structural isomerism should stimulate attention toward advanced design and synthesis of functional nanomaterials enabled by structural transformations.

Abstract

Few structural isomers of colloids, with identical masses but different structures, have been identified. Here, the authors observe an interesting example of structural isomerism in a pair of semiconductor magic-size clusters, which reversibly transform between one another with first-order unimolecular reaction kinetics.