Effect of Perylene Photosensitizer Attachment to [Pd(triphosphine)L]2+ on CO2 Electrocatalysis

Rita E. Cook, Brian T. Phelan, Leah E. Shoer, Marek B. Majewski, Michael R Wasielewski

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Two new covalently linked chromophore-CO2 reduction catalyst systems were prepared using a perylene chromophore and a bis[(dicyclohexylphosphino)ethyl]phenylphosphinopalladium(II) catalyst. The primary goal of this study is to probe the influence of photosensitizer attachment on the electrocatalytic performance. The position either para or meta to the phosphorus on the phenyl group of the palladium complex was linked via a 2,5-xylyl group to the 3 position of perylene. The electrocatalytic CO2 reduction activity of the palladium complex is maintained in the meta-linked system, but is lost in the para-linked system, possibly because of unfavorable interactions of the perylene chromophore with the glassy carbon electrode used. Following selective photoexcitation of the perylene, an enhanced perylene excited-state decay rate was observed in the palladium complexes compared to perylene attached to the free ligands. This decrease is accompanied by formation of the perylene cation radical, showing that electron transfer from perylene to the palladium catalyst occurs. Electron transfer and charge recombination were both found to be faster in the para-linked system than in the meta-linked one, which is attributed to stronger electronic coupling in the former. These results illustrate the need to carefully tune the electronic coupling between a photosensitizer chromophore and the catalyst to promote photodriven electron transfer yet inhibit adverse electronic effects of the chromophore on electrocatalysis.

Original languageEnglish
Pages (from-to)12281-12289
Number of pages9
JournalInorganic Chemistry
Volume55
Issue number23
DOIs
Publication statusPublished - Dec 5 2016

Fingerprint

Perylene
Electrocatalysis
Photosensitizing Agents
chromophores
attachment
palladium
Chromophores
Palladium
catalysts
electron transfer
Catalysts
electronics
glassy carbon
Electrons
photoexcitation
decay rates
phosphorus
Photoexcitation
Glassy carbon
cations

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Effect of Perylene Photosensitizer Attachment to [Pd(triphosphine)L]2+ on CO2 Electrocatalysis. / Cook, Rita E.; Phelan, Brian T.; Shoer, Leah E.; Majewski, Marek B.; Wasielewski, Michael R.

In: Inorganic Chemistry, Vol. 55, No. 23, 05.12.2016, p. 12281-12289.

Research output: Contribution to journalArticle

Cook, Rita E. ; Phelan, Brian T. ; Shoer, Leah E. ; Majewski, Marek B. ; Wasielewski, Michael R. / Effect of Perylene Photosensitizer Attachment to [Pd(triphosphine)L]2+ on CO2 Electrocatalysis. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 23. pp. 12281-12289.
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