A single thiolate ligand modulates the core structure and stability of non-magic-numbered cadmium-sulfide clusters [Cd9S4(SPh)12– x ](2– x )– ( x = 0, 1)
Year: 2026
Type: article
Abstract: Semiconductor clusters with magic-numbered compositions have attracted considerable interest as ideal model systems in nanochemistry, whereas those with non-magic-numbered compositions remain poorly understood because of their limited accessibility by wet-chemical synthesis. Here, we generated thiolate-protected cadmium-sulfide clusters with non-magic-numbered compositions, [Cd9S4(SPh)12]2– (Cd9) and [Cd9S4(SPh)11]– (Cd9'), in the gas phase upon electrospray ionization of [Cd10S4(SPh)16](NMe4)4 and investigated the collision-induced dissociation (CID) behaviors. Both Cd9 and Cd9' yielded the same major dissociation product [Cd8S4(SPh)9]–; however, the dissociation threshold energy for Cd9' was markedly higher, by ca. 0.3 eV, than that for Cd9. Density functional theory (DFT) calculations revealed that Cd9 retains a highly symmetric pyramidal core closely related to that of the parent magic-numbered cluster, whereas Cd9' prefers a more distorted core with increased local Cd–S bonds. These results indicate that a difference of one thiolate ligand alters not only the core structure and resistance to dissociation but also the balance between symmetry-driven and bond-driven stabilization factors. This study highlights ligand coverage as an effective factor for tuning the geometric structure and stability of ligand-protected semiconductor clusters.
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $2,040
OpenAlex ID: W7204216216
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