Size-Dependent Janus-Ligand Shell Formation on PbS Quantum Dots

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We studied the size-dependent Janus ligand shell formation on PbS QDs employing an X-type ligand exchange reaction between native oleate ligands and two substituted cinnamic acid ligands, trifluoromethyl- and dimethyl amino-cinnamic acid, representing electron donating and electron withdrawing ligands. The exchange reactions become significantly more favorable for both electron donating and withdrawing ligands (ΔGbecomes more negative) in the smaller QDs compared to the larger QDs likely because the ligand density is smaller on the larger QDs reducing the strength of the ligand-ligand interactions. We found that Janus-ligand shells form more readily on smaller QDs than on bigger QDs with electron donating ligands. We also observed a dependence on the QD concentration that should be considered when forming Janus-ligand shells. Two-dimensional solution nuclear magnetic resonance spectroscopy (2D-NMR) shows evidence of pronounced phase segregation between oleate and electron donating ligands on the smaller QDs consistent with the enhanced ligand-ligand interactions. This study broadens our understanding of how to construct Janus and patchy ligand shell morphologies on small QDs.

Original languageAmerican English
Pages (from-to)21729-21739
Number of pages11
JournalJournal of Physical Chemistry C
Issue number39
StatePublished - 7 Oct 2021

Bibliographical note

Publisher Copyright:
© 2021 American Chemical Society

NREL Publication Number

  • NREL/JA-5900-79823


  • Janus ligand shells
  • PbS QDs
  • solar-photochemistry


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