We report the first observation of the reversible transformations that occur among three types of CdTe magic-size clusters (MSCs) in dispersion at room temperature and discuss our understanding of the transformation pathway. The reversible transformations were achieved with CdTe prenucleation stage samples, which were prepared with reactions of cadmium oleate [Cd(OA) 2 ] and tri-n-octylphosphine telluride in 1-octadecene and were then dispersed in mixtures of toluene and a primary amine at room temperature. Three types of OA-passivated CdTe MSCs evolved, exhibiting sharp optical absorption singlets peaking at 371, 417, and 448 nm. The MSCs and their immediate precursor compounds (PCs; with no sharp optical absorption) are labeled by the MSC absorption peak wavelengths. The transformation between MSC-371 and MSC-417 has a distinct isosbestic point at ∼385 nm and that between MSC-417 and MSC-448 at ∼430 nm. Our findings suggest that these PC-enabled reversible transformations occur through a process of quasi-isomerization, transforming between PCs and their counterpart MSCs, combined with substitution reactions that cause transformation between the two involved PCs.

The transformations of colloidal semiconductor magic-size clusters (MSCs) are expected to occur with only discrete, step-wise redshifts in optical absorption. Here, we challenge this assumption presenting a novel, conceptually different transformation, for which the redshift is continuous. In the room-temperature transformation from CdTe MSC-448 to MSC-488 (designated by the peak wavelengths in nanometer), the redshift of absorption monitored in situ displays distinctly continuous and/or step-wise behavior. Based on conclusive evidence provided by real-time experiments, the former transformation is apparently direct and intracluster with a relatively large energy barrier. The latter transformation is indirect and assisted by MSC precursor compounds (PCs). The former transformation follows the latter often, being predominant at a relatively high temperature. The present findings encourage a reconsideration of the absorption redshift reported previously for transformations of binary II-VI MSCs, together with the pathway associated without the increase of cluster mass.

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The field of isomerization reactions for colloidal semiconductor magic-size clusters (MSCs) remains largely unexplored. Here, we show that MSCs isomerize via two fundamental pathways that are regulated by the acidity and amount of an incoming ligand, with CdTeSe as the model system. When MSC-399 isomerizes to MSC-422 at room temperature, the peak red-shift from 399 to 422 nm is continuous (pathway 1) and/or stepwise (pathway 2) as monitored in situ and in real time by optical absorption spectroscopy. We propose that pathway 1 is direct, with intracluster configuration changes and a relatively large energy barrier. Pathway 2 is indirect, assisted by the MSC precursor compounds (PCs), from MSC-399 to PC-399 to PC-422 to MSC-422. Pathway 1 is activated when PC-422 to MSC-422 is suppressed. Our findings unambiguously suggest that when a change occurs directly on a nanospecies, its absorption peak continuously shifts. The present study provides an in-depth understanding of the transformative behavior of MSCs via ligand-induced isomerization upon external chemical stimuli.

The transformations of colloidal semiconductor magic‐size clusters (MSCs) are expected to occur with only discrete, step‐wise redshifts in optical absorption. Here, we challenge this assumption presenting a novel, conceptually different transformation, for which the redshift is continuous. In the room‐temperature transformation from CdTe MSC‐448 to MSC‐488 (designated by the peak wavelengths in nanometer), the redshift of absorption monitored in situ displays distinctly continuous and/or step‐wise behavior. Based on conclusive evidence provided by real‐time experiments, the former transformation is apparently direct and intra‐cluster with a relatively large energy barrier. The latter transformation is indirect and assisted by MSC precursor compounds (PCs). The former transformation follows the latter often, being predominant at a relatively high temperature. The present findings encourage a reconsideration of the absorption redshift reported previously for transformations of binary II–VI MSCs, together with the pathway associated without the increase of cluster mass.