Effect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO) 3 X

Jose F. Martinez, Nathan T. La Porte, Subhajyoti Chaudhuri, Alessandro Sinopoli, Youn Jue Bae, Muhammad Sohail, Victor S. Batista, Michael R Wasielewski

Research output: Contribution to journalArticle

Abstract

The electron transfer rate between a donor and an acceptor depends on the free energy change for the reaction as well as differences in structure and electronic coupling between the initial and final states. Selective excitation of a naphthalenediimide radical anion (NDI •- ) covalently linked at the 4-, 5-, or 6-positions of the bipyridine (bpy) in the Re(bpy)(CO) 3 X (X = Cl or pyridine) carbon dioxide reduction catalyst results in electron transfer from 2 NDI •- to Re(bpy)(CO) 3 X to form Re(bpy •- )(CO) 3 X, the first intermediate in the photocatalytic reduction of CO 2 . Femtosecond UV/vis, near-IR, and mid-IR spectroscopy on these constitutional isomers and a set of appropriate reference molecules show that systematically varying the electronic coupling as well as the reaction free energy increases the lifetime of Re(bpy •- )(CO) 3 X by an order of magnitude when the NDI chromophore is attached to the 6-position of bpy. NMR and X-ray structural studies along with computational modeling are used to identify the conformation of Re(6-NDI-bpy)(CO) 3 X responsible for these favorable changes. Extending the lifetime of the reduced complex in the covalent photosensitizer-catalyst assembly is a critical requirement for the photocatalytic CO 2 reduction and artificial photosynthesis.

Original languageEnglish
Pages (from-to)10178-10190
Number of pages13
JournalJournal of Physical Chemistry C
Volume123
Issue number16
DOIs
Publication statusPublished - Apr 25 2019

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Carbon Monoxide
Anions
electron transfer
Negative ions
anions
Free energy
Electrons
free energy
electronics
catalysts
life (durability)
Catalysts
Photosensitizers
photosynthesis
Photosynthesis
Chromophores
Isomers
Pyridine
chromophores
Conformations

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Effect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO) 3 X . / Martinez, Jose F.; La Porte, Nathan T.; Chaudhuri, Subhajyoti; Sinopoli, Alessandro; Bae, Youn Jue; Sohail, Muhammad; Batista, Victor S.; Wasielewski, Michael R.

In: Journal of Physical Chemistry C, Vol. 123, No. 16, 25.04.2019, p. 10178-10190.

Research output: Contribution to journalArticle

Martinez, Jose F. ; La Porte, Nathan T. ; Chaudhuri, Subhajyoti ; Sinopoli, Alessandro ; Bae, Youn Jue ; Sohail, Muhammad ; Batista, Victor S. ; Wasielewski, Michael R. / Effect of Electronic Coupling on Electron Transfer Rates from Photoexcited Naphthalenediimide Radical Anion to Re(bpy)(CO) 3 X In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 16. pp. 10178-10190.
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