Fast triplet formation via singlet exciton fission in a covalent perylenediimide-β-apocarotene dyad aggregate

Catherine M. Mauck, Kristen E. Brown, Noah E. Horwitz, Michael R Wasielewski

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A covalent dyad was synthesized in which perylene-3,4,:9:10-bis(dicarboximide) (PDI) is linked to β-apocarotene (Car) using a biphenyl spacer. The dyad is monomeric in toluene and forms a solution aggregate in methylcyclohexane (MCH). Using femtosecond transient absorption (fsTA) spectroscopy, the monomeric dyad and its aggregates were studied both in solution and in thin films. In toluene, photoexcitation at 530 nm preferentially excites PDI, and the dyad undergoes charge separation in τ = 1.7 ps and recombination in τ = 1.6 ns. In MCH and in thin solid films, 530 nm excitation of the PDI-Car aggregate also results in charge transfer that competes with energy transfer from 1 PDI to Car and with an additional process, rapid Car triplet formation in 3∗PDI to the carotenoid. SF from β-apocarotene aggregation is ruled out by direct excitation of Car films at 414 nm, where no triplet formation is observed. Time-resolved electron paramagnetic resonance measurements on aggregated PDI-Car show the formation of 3∗Car with a spin-polarization pattern that rules out radical-pair intersystem crossing as the mechanism of triplet formation as well.

Original languageEnglish
Pages (from-to)5587-5596
Number of pages10
JournalJournal of Physical Chemistry A
Volume119
Issue number22
DOIs
Publication statusPublished - Jun 4 2015

Fingerprint

fission
Railroad cars
excitons
toluene
Toluene
carotenoids
polarization (charge separation)
photoexcitation
Perylene
spacers
excitation
electron paramagnetic resonance
absorption spectroscopy
Spin polarization
Photoexcitation
energy transfer
charge transfer
Carotenoids
Absorption spectroscopy
Energy transfer

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fast triplet formation via singlet exciton fission in a covalent perylenediimide-β-apocarotene dyad aggregate. / Mauck, Catherine M.; Brown, Kristen E.; Horwitz, Noah E.; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 119, No. 22, 04.06.2015, p. 5587-5596.

Research output: Contribution to journalArticle

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