Large Dipolar Spin - Spin Interaction in a Photogenerated U-Shaped Triradical

Daniel M. Gardner, Hsiao Fan Chen, Matthew D. Krzyaniak, Mark A Ratner, Michael R Wasielewski

Research output: Contribution to journalArticle

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Abstract

Transient electron paramagnetic resonance (TREPR) spectroscopy has been used to study the spin - spin interactions in a novel U-shaped electron donor - chromophore - acceptor - radical (D - C - A - R) system in which a xanthene bridge holds a tert-butylphenyl nitroxide (BPNO) radical in close proximity to a naphthalene-1,8:4,5-bis(dicarboximide) (NDI) acceptor. Photoexcitation of the 4-aminonaphthalene-1,8-dicarboximide (ANI) chromophore results in rapid, two-step electron transfer to generate the triradical (D+• - C - A-• - R). The large through-bond distance between A-• and R makes their spin - spin exchange interaction (2JAR) negligibly small, whereas their short through-space distance results in a strong dipolar interaction (DAR), which is observed as a set of broad lines in the TREPR spectra of D+• - C - A-• - R in solid toluene solution at 85 K. Transient nutation experiments show that these transitions belong to a species with spin S = 1, whereas experiments on D+• - C - A-• - R in the oriented nematic liquid crystal 4-cyano-4′-n-pentylbiphenyl at 85 K demonstrate the anisotropy of DAR. (Figure Presented)

Original languageEnglish
Pages (from-to)8040-8048
Number of pages9
JournalJournal of Physical Chemistry A
Volume119
Issue number29
DOIs
Publication statusPublished - Jul 23 2015

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Chromophores
Paramagnetic resonance
Xanthenes
1-Naphthylamine
chromophores
electron paramagnetic resonance
Electrons
Nematic liquid crystals
Photoexcitation
Exchange interactions
Toluene
interactions
nutation
spin exchange
Anisotropy
Experiments
photoexcitation
naphthalene
Spectroscopy
toluene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Large Dipolar Spin - Spin Interaction in a Photogenerated U-Shaped Triradical. / Gardner, Daniel M.; Chen, Hsiao Fan; Krzyaniak, Matthew D.; Ratner, Mark A; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 119, No. 29, 23.07.2015, p. 8040-8048.

Research output: Contribution to journalArticle

Gardner, Daniel M. ; Chen, Hsiao Fan ; Krzyaniak, Matthew D. ; Ratner, Mark A ; Wasielewski, Michael R. / Large Dipolar Spin - Spin Interaction in a Photogenerated U-Shaped Triradical. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 29. pp. 8040-8048.
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