Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor

Svante Hedström, Subhajyoti Chaudhuri, Nathan T. La Porte, Benjamin Rudshteyn, Jose F. Martinez, Michael R. Wasielewski*, Victor S. Batista

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


Spin-dependent intramolecular electron transfer is revealed in the ReI(CO)3(py)(bpy-Ph)-perylenediimide radical anion (ReI-bpy-PDI-•) dyad, a prototype model system for artificial photosynthesis. Quantum chemical calculations and ultrafast transient absorption spectroscopy experiments demonstrate that selective photoexcitation of ReI-bpy results in electron transfer from PDI-• to ReI-bpy, forming two distinct charge-shifted states. One is an overall doublet whose return to the ground state is spin-allowed. The other, high-spin quartet state, persists for 67 ns due to spin-forbidden back-electron transfer, constituting a more than thousandfold lifetime improvement compared to the low-spin state. Exploiting this spin dependency holds promise for artificial photosynthetic systems requiring long-lived reduced states to perform multi-electron chemistry.

Original languageEnglish (US)
Pages (from-to)16466-16469
Number of pages4
JournalJournal of the American Chemical Society
Issue number46
StatePublished - Nov 22 2017

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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