Ultrafast electron-transfer in a fully conjugated coumarin-ferrocene donor-acceptor dyads

Alex J. King, Yuriy V. Zatsikha, Tanner Blessener, Forrest Dalbec, Philip C. Goff, Mathew Kayser, David A Blank, Yuriy P. Kovtun, Victor N. Nemykin

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

A series of a fully conjugated ferrocene-containing coumarins and B,O-chelated coumarins was prepared and characterized by a variety of spectroscopic (UV–vis, NMR, and mass spectrometry), electrochemical (CV and DPV) and spectroelectrochemical methods. The photophysical properties of the target compounds were investigated by steady-state fluorescence and ultrafast transient absorption spectroscopy methods. Selective photoexcitation of the coumarin core was followed by ultrafast electron transfer from the ferrocene fragment, resulting in formation of a charge-separated Fc+-coumarin-. state. This charge-separated state undergoes ultrafast ground state recovery in 20–25 ps, shortening the excited state lifetime of the organic coumarin precursors (1.2–1.5 ns) by almost two orders of magnitude. Formation of the charge-separated states was supported by the experimental (steady-state fluorescence oxidative titrations) and theoretical DFT and TDDFT calculations.

Original languageEnglish (US)
Pages (from-to)86-97
Number of pages12
JournalJournal of Organometallic Chemistry
Volume887
DOIs
StatePublished - May 1 2019

Bibliographical note

Funding Information:
Generous support from the Minnesota Supercomputing Institute, NSERC , CFI , NSF ( CHE-1464711 and MRI-1420373 ) University of Manitoba , and WestGrid Canada to VN is greatly appreciated. Generous support from the NSF ( DMR-1708177 ) to DAB is greatly appreciated.

Funding Information:
Generous support from the Minnesota Supercomputing Institute, NSERC, CFI, NSF (CHE-1464711 and MRI-1420373) University of Manitoba, and WestGrid Canada to VN is greatly appreciated. Generous support from the NSF (DMR-1708177) to DAB is greatly appreciated.

Publisher Copyright:
© 2019 Elsevier B.V.

Keywords

  • Coumarin
  • Density functional theory
  • Ferrocene
  • Transient absorption spectroscopy

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