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

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

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
Pages (from-to)16466-16469
Number of pages4
JournalJournal of the American Chemical Society
Volume139
Issue number46
DOIs
Publication statusPublished - Nov 22 2017

Fingerprint

Carbon Monoxide
Anions
Negative ions
Electrons
Photosynthesis
Photoexcitation
Absorption spectroscopy
Ground state
Spectrum Analysis
perylenediimide
Experiments

ASJC Scopus subject areas

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

Cite this

Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor. / Hedström, Svante; Chaudhuri, Subhajyoti; La Porte, Nathan T.; Rudshteyn, Benjamin; Martinez, Jose F.; Wasielewski, Michael R; Batista, Victor S.

In: Journal of the American Chemical Society, Vol. 139, No. 46, 22.11.2017, p. 16466-16469.

Research output: Contribution to journalArticle

Hedström, Svante ; Chaudhuri, Subhajyoti ; La Porte, Nathan T. ; Rudshteyn, Benjamin ; Martinez, Jose F. ; Wasielewski, Michael R ; Batista, Victor S. / Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 46. pp. 16466-16469.
@article{e3b0e87a79da4a368fff5a1f9d066ae7,
title = "Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor",
abstract = "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.",
author = "Svante Hedstr{\"o}m and Subhajyoti Chaudhuri and {La Porte}, {Nathan T.} and Benjamin Rudshteyn and Martinez, {Jose F.} and Wasielewski, {Michael R} and Batista, {Victor S.}",
year = "2017",
month = "11",
day = "22",
doi = "10.1021/jacs.7b09438",
language = "English",
volume = "139",
pages = "16466--16469",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "46",

}

TY - JOUR

T1 - Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)3 via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor

AU - Hedström, Svante

AU - Chaudhuri, Subhajyoti

AU - La Porte, Nathan T.

AU - Rudshteyn, Benjamin

AU - Martinez, Jose F.

AU - Wasielewski, Michael R

AU - Batista, Victor S.

PY - 2017/11/22

Y1 - 2017/11/22

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85034854187&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85034854187&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b09438

DO - 10.1021/jacs.7b09438

M3 - Article

VL - 139

SP - 16466

EP - 16469

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 46

ER -