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

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)

Fingerprint Dive into the research topics of 'Electron transfer from photoexcited naphthalene-1,4:5,8-bis(dicarboximide) radical anion to Mn(bpy)(CO)<sub>3</sub>X and Re(bpy)(CO)<sub>3</sub>X CO<sub>2</sub> reduction catalysts linked via a saturated methylene bridge'. Together they form a unique fingerprint.

  • Cite this