Quantum Dots Photocatalyze Intermolecular [2 + 2] Cycloadditions of Aromatic Alkenes Adsorbed to their Surfaces via van der Waals Interactions

Yishu Jiang, Rafael López-Arteaga, Emily A. Weiss*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

Triplet excited state-initiated photochemistry is a mild and selective route to cycloadditions, radical rearrangements, couplings, fragmentations, and isomerizations. Colloidal quantum dots are proven visible-light photosensitizers and structural scaffolds for triplet-initiated reactions of molecules that are functionalized (with carboxylates) to anchor on the QD surface. Here, with the aid of polyaromatic energy shuttles that act as noncovalent adsorption sites for substrates on the QD surface, the scope of QD-photocatalyzed intermolecular [2 + 2] cycloadditions is extended to freely diffusing substrates (no anchoring groups). QD-shuttle complexes photocatalyze homo- and heterointermolecular [2 + 2] photocycloadditions of benzalacetone, chalcone and its derivatives with up to 94% yield; the yields for all reactions are comparable to those achieved by Ir(ppy)3 but with the advantages of a factor of 2.5 lower catalyst loading, superior stability, and the ability to recover the catalyst by simple centrifugation and reuse it for multiple reaction cycles. Experiments imply a two-step triplet-triplet energy transfer mechanism, one energy transfer from the QD to the energy shuttle followed by a second energy transfer from the shuttle to the transiently adsorbed substrate.

Original languageEnglish (US)
Pages (from-to)3782-3786
Number of pages5
JournalJournal of the American Chemical Society
Volume144
Issue number9
DOIs
StatePublished - Mar 9 2022

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'Quantum Dots Photocatalyze Intermolecular [2 + 2] Cycloadditions of Aromatic Alkenes Adsorbed to their Surfaces via van der Waals Interactions'. Together they form a unique fingerprint.

Cite this