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

doi:10.1021/jacs.7b09438

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 journal › Article › peer-review

19 Scopus citations

Abstract

Spin-dependent intramolecular electron transfer is revealed in the Re^I(CO)₃(py)(bpy-Ph)-perylenediimide radical anion (Re^I-bpy-PDI^-•) dyad, a prototype model system for artificial photosynthesis. Quantum chemical calculations and ultrafast transient absorption spectroscopy experiments demonstrate that selective photoexcitation of Re^I-bpy results in electron transfer from PDI^-• to Re^I-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 language	English (US)
Pages (from-to)	16466-16469
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	46
DOIs	https://doi.org/10.1021/jacs.7b09438
State	Published - Nov 22 2017

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.7b09438

Cite this

Hedström, S., Chaudhuri, S., La Porte, N. T., Rudshteyn, B., Martinez, J. F., Wasielewski, M. R., & Batista, V. S. (2017). Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)₃ via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor. Journal of the American Chemical Society, 139(46), 16466-16469. https://doi.org/10.1021/jacs.7b09438

@article{c625638984f14c8ebec10035cc1232cf,

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.}",

note = "Funding Information: This work was supported by ANSER, an Energy Frontier Research Center funded by the U.S. DOE under Award No. DE-SC0001059 and by a generous donation from the TomKat foundation. B.R. is supported by the NSFGRFP under Grant No. DGE-1122492. For computer resources, we thank Yale HPC and XSEDE. Brian T. Phelan assisted with collection of the transient absorption data. Dr. Atanu Acharya supplied the pairwise Coulomb-interaction code. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = nov,

day = "22",

doi = "10.1021/jacs.7b09438",

language = "English (US)",

volume = "139",

pages = "16466--16469",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "46",

}

Hedström, S, Chaudhuri, S, La Porte, NT, Rudshteyn, B, Martinez, JF, Wasielewski, MR & Batista, VS 2017, 'Thousandfold Enhancement of Photoreduction Lifetime in Re(bpy)(CO)₃ via Spin-Dependent Electron Transfer from a Perylenediimide Radical Anion Donor', Journal of the American Chemical Society, vol. 139, no. 46, pp. 16466-16469. https://doi.org/10.1021/jacs.7b09438

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. et al.

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

Research output: Contribution to journal › Article › peer-review

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.

N1 - Funding Information: This work was supported by ANSER, an Energy Frontier Research Center funded by the U.S. DOE under Award No. DE-SC0001059 and by a generous donation from the TomKat foundation. B.R. is supported by the NSFGRFP under Grant No. DGE-1122492. For computer resources, we thank Yale HPC and XSEDE. Brian T. Phelan assisted with collection of the transient absorption data. Dr. Atanu Acharya supplied the pairwise Coulomb-interaction code. Publisher Copyright: © 2017 American Chemical Society.

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

C2 - 29083146

AN - SCOPUS:85034854187

SN - 0002-7863

VL - 139

SP - 16466

EP - 16469

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 46

ER -

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

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this