Intersystem crossing mediated by photoinduced intramolecular charge transfer: Julolidine - Anthracene molecules with perpendicular π systems

Zachary E X Dance, Sarah M. Mickley, Thea M. Wilson, Annie Butler Ricks, Amy M. Scott, Mark A Ratner, Michael R Wasielewski

Research output: Contribution to journalArticle

87 Citations (Scopus)

Abstract

Time-resolved electron paramagnetic resonance studies show that the primary mechanism of triplet formation following photoexcitation of julolidine-anthracene molecules linked by a single bond and having perpendicular π systems is a spin-orbit, charge-transfer intersystem crossing mechanism (SOCT - ISC). This mechanism depends on the degree of charge transfer from julolidine to anthracene, the dihedral angle (θ1) between their π systems, and the magnitude of the electronic coupling between julolidine and anthracene. We compare 4-(9-anthracenyl)-julolidine with the more sterically encumbered 4-(9-anthracenyl)-3,5-dimethyrjulolidine and find that fixing θ1 ≅ 90° serves to enhance SOCT - ISC by increasing the change in orbital angular momentum accompanying charge transfer. Given that the requirements for the SOCT - ISC mechanism are quite general, we expect it to occur in a variety of electron donor-acceptor systems.

Original languageEnglish
Pages (from-to)4194-4201
Number of pages8
JournalJournal of Physical Chemistry A
Volume112
Issue number18
DOIs
Publication statusPublished - May 8 2008

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anthracene
Charge transfer
charge transfer
Molecules
Orbits
molecules
orbits
Photoexcitation
Angular momentum
Dihedral angle
Paramagnetic resonance
photoexcitation
fixing
dihedral angle
electron paramagnetic resonance
angular momentum
Electrons
orbitals
requirements
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Intersystem crossing mediated by photoinduced intramolecular charge transfer : Julolidine - Anthracene molecules with perpendicular π systems. / Dance, Zachary E X; Mickley, Sarah M.; Wilson, Thea M.; Ricks, Annie Butler; Scott, Amy M.; Ratner, Mark A; Wasielewski, Michael R.

In: Journal of Physical Chemistry A, Vol. 112, No. 18, 08.05.2008, p. 4194-4201.

Research output: Contribution to journalArticle

Dance, Zachary E X ; Mickley, Sarah M. ; Wilson, Thea M. ; Ricks, Annie Butler ; Scott, Amy M. ; Ratner, Mark A ; Wasielewski, Michael R. / Intersystem crossing mediated by photoinduced intramolecular charge transfer : Julolidine - Anthracene molecules with perpendicular π systems. In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 18. pp. 4194-4201.
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