Direct Observation of the Photoreduction Products of Mn(NDI-bpy)(CO) 3 X CO 2 Reduction Catalysts Using Femtosecond Transient IR Spectroscopy

Jose F. Martinez, Nathan T. La Porte, Ryan M. Young, Alessandro Sinopoli, Muhammad Sohail, Michael R Wasielewski

Research output: Contribution to journalArticle

Abstract

The electrochemical reduction of the Mn(bpy)(CO) 3 X CO 2 reduction catalyst is thought to proceed by the initial reduction of Mn I to Mn 0 . We have covalently attached a naphthalenediimide radical anion (NDI •- ) chromophore to the 4-, 5-, or 6-position of the bpy via a phenyl bridge to produce Mn(NDI •- -bpy)(CO) 3 X, where X = Br, CH 3 CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron-transfer reactions following selective photoexcitation of NDI •- to its lowest excited doublet state, 2∗ NDI •- . In complexes where NDI •- is attached at the 4- or 5-position of bipyridine, only the reaction Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X is observed, whereas in the complex where NDI •- is attached to the 6-position of bipyridine, the reaction sequence Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X → Mn 0 (NDI-bpy)(CO) 3 is observed. Moreover, in the complexes with an NDI •- bound to the 6-position of bipyridine, Mn 0 (NDI-bpy)(CO) 3 exhibits a lifetime that is ∼10 5 times longer than those in complexes with an NDI •- bound at the four- or five-position of the bipyridine.

Original languageEnglish
Pages (from-to)6416-6426
Number of pages11
JournalJournal of Physical Chemistry C
Volume123
Issue number11
DOIs
Publication statusPublished - Mar 21 2019

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Carbon Monoxide
photochemical reactions
Infrared spectroscopy
catalysts
Catalysts
products
spectroscopy
Photoexcitation
Chromophores
Excited states
Negative ions
Electrons
photoexcitation
chromophores
electron transfer
methylidyne
anions
life (durability)
Anions
excitation

ASJC Scopus subject areas

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

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Direct Observation of the Photoreduction Products of Mn(NDI-bpy)(CO) 3 X CO 2 Reduction Catalysts Using Femtosecond Transient IR Spectroscopy . / Martinez, Jose F.; La Porte, Nathan T.; Young, Ryan M.; Sinopoli, Alessandro; Sohail, Muhammad; Wasielewski, Michael R.

In: Journal of Physical Chemistry C, Vol. 123, No. 11, 21.03.2019, p. 6416-6426.

Research output: Contribution to journalArticle

Martinez, Jose F. ; La Porte, Nathan T. ; Young, Ryan M. ; Sinopoli, Alessandro ; Sohail, Muhammad ; Wasielewski, Michael R. / Direct Observation of the Photoreduction Products of Mn(NDI-bpy)(CO) 3 X CO 2 Reduction Catalysts Using Femtosecond Transient IR Spectroscopy In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 11. pp. 6416-6426.
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abstract = "The electrochemical reduction of the Mn(bpy)(CO) 3 X CO 2 reduction catalyst is thought to proceed by the initial reduction of Mn I to Mn 0 . We have covalently attached a naphthalenediimide radical anion (NDI •- ) chromophore to the 4-, 5-, or 6-position of the bpy via a phenyl bridge to produce Mn(NDI •- -bpy)(CO) 3 X, where X = Br, CH 3 CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron-transfer reactions following selective photoexcitation of NDI •- to its lowest excited doublet state, 2∗ NDI •- . In complexes where NDI •- is attached at the 4- or 5-position of bipyridine, only the reaction Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X is observed, whereas in the complex where NDI •- is attached to the 6-position of bipyridine, the reaction sequence Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X → Mn 0 (NDI-bpy)(CO) 3 is observed. Moreover, in the complexes with an NDI •- bound to the 6-position of bipyridine, Mn 0 (NDI-bpy)(CO) 3 exhibits a lifetime that is ∼10 5 times longer than those in complexes with an NDI •- bound at the four- or five-position of the bipyridine.",
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AU - Sinopoli, Alessandro

AU - Sohail, Muhammad

AU - Wasielewski, Michael R

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N2 - The electrochemical reduction of the Mn(bpy)(CO) 3 X CO 2 reduction catalyst is thought to proceed by the initial reduction of Mn I to Mn 0 . We have covalently attached a naphthalenediimide radical anion (NDI •- ) chromophore to the 4-, 5-, or 6-position of the bpy via a phenyl bridge to produce Mn(NDI •- -bpy)(CO) 3 X, where X = Br, CH 3 CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron-transfer reactions following selective photoexcitation of NDI •- to its lowest excited doublet state, 2∗ NDI •- . In complexes where NDI •- is attached at the 4- or 5-position of bipyridine, only the reaction Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X is observed, whereas in the complex where NDI •- is attached to the 6-position of bipyridine, the reaction sequence Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X → Mn 0 (NDI-bpy)(CO) 3 is observed. Moreover, in the complexes with an NDI •- bound to the 6-position of bipyridine, Mn 0 (NDI-bpy)(CO) 3 exhibits a lifetime that is ∼10 5 times longer than those in complexes with an NDI •- bound at the four- or five-position of the bipyridine.

AB - The electrochemical reduction of the Mn(bpy)(CO) 3 X CO 2 reduction catalyst is thought to proceed by the initial reduction of Mn I to Mn 0 . We have covalently attached a naphthalenediimide radical anion (NDI •- ) chromophore to the 4-, 5-, or 6-position of the bpy via a phenyl bridge to produce Mn(NDI •- -bpy)(CO) 3 X, where X = Br, CH 3 CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron-transfer reactions following selective photoexcitation of NDI •- to its lowest excited doublet state, 2∗ NDI •- . In complexes where NDI •- is attached at the 4- or 5-position of bipyridine, only the reaction Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X is observed, whereas in the complex where NDI •- is attached to the 6-position of bipyridine, the reaction sequence Mn( 2∗ NDI •- -bpy)(CO) 3 X → Mn(NDI-bpy •- )(CO) 3 X → Mn 0 (NDI-bpy)(CO) 3 is observed. Moreover, in the complexes with an NDI •- bound to the 6-position of bipyridine, Mn 0 (NDI-bpy)(CO) 3 exhibits a lifetime that is ∼10 5 times longer than those in complexes with an NDI •- bound at the four- or five-position of the bipyridine.

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