Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)3X and Re(bpy)(CO)3X CO2 reduction catalysts linked via a saturated methylene bridge

Jose F. Martinez, Nathan T. La Porte, Michael R Wasielewski

Research output: Contribution to journalArticle

Abstract

Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•− results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy•−)(CO)3X and Re(I)(bpy•−)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy•−)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.

Original languageEnglish
Pages (from-to)21-28
Number of pages8
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume372
DOIs
Publication statusPublished - Mar 1 2019

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Carbon Monoxide
Naphthalene
naphthalene
methylene
Anions
electron transfer
Negative ions
anions
catalysts
ligands
Catalysts
Electrons
photoexcitation
Ligands
unity
Photoexcitation
infrared spectroscopy
Quantum yield
Metal complexes
Infrared spectroscopy

Keywords

  • CO reduction
  • Electrochemistry
  • Electron transfer
  • Femtosecond spectroscopy
  • Radical anions
  • Solar energy

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Physics and Astronomy(all)

Cite this

@article{d69974f5ec3d4060a37e6089171766d7,
title = "Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)3X and Re(bpy)(CO)3X CO2 reduction catalysts linked via a saturated methylene bridge",
abstract = "Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•− results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy•−)(CO)3X and Re(I)(bpy•−)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy•−)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.",
keywords = "CO reduction, Electrochemistry, Electron transfer, Femtosecond spectroscopy, Radical anions, Solar energy",
author = "Martinez, {Jose F.} and {La Porte}, {Nathan T.} and Wasielewski, {Michael R}",
year = "2019",
month = "3",
day = "1",
doi = "10.1016/j.jphotochem.2018.11.047",
language = "English",
volume = "372",
pages = "21--28",
journal = "Journal of Photochemistry and Photobiology A: Chemistry",
issn = "1010-6030",
publisher = "Elsevier",

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TY - JOUR

T1 - Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)3X and Re(bpy)(CO)3X CO2 reduction catalysts linked via a saturated methylene bridge

AU - Martinez, Jose F.

AU - La Porte, Nathan T.

AU - Wasielewski, Michael R

PY - 2019/3/1

Y1 - 2019/3/1

N2 - Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•− results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy•−)(CO)3X and Re(I)(bpy•−)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy•−)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.

AB - Supramolecular systems that connect a naphthalene-1,4:5,8-bis(dicarboximide) (NDI) radical anion donor to Mn(bpy)(CO)3Br or Re(bpy)(CO)3Cl CO2 reduction catalysts via a methylene bridge have been synthesized and studied by femtosecond transient visible, near-infrared and mid-infrared spectroscopy. The use of the methylene bridge to link NDI to the complexes does not affect the reduction potentials of the metal complexes. Selective photoexcitation of NDI•− to 2*NDI•− results in ultrafast reduction of the bipyridine (bpy) ligands on both the Mn and Re complexes to form Mn(I)(bpy•−)(CO)3X and Re(I)(bpy•−)(CO)3X in near unity quantum yield, respectively. The initial formation of Mn(I)(bpy•−)(CO)3X is unexpected based on previous electrochemical data that indicates the Mn(I) center is reduced at a more positive potential than the bpy ligand. Moreover, the rate of forward electron transfer in the Mn complex was found to be faster than in the Re complex, while the rate of the back electron transfer in the Re complex was faster than in the Mn complex.

KW - CO reduction

KW - Electrochemistry

KW - Electron transfer

KW - Femtosecond spectroscopy

KW - Radical anions

KW - Solar energy

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