Evidence for Charge-Transfer Mediation in the Primary Events of Singlet Fission in a Weakly Coupled Pentacene Dimer

Journal article


Publication Details

Author(s): Basel B, Zirzlmeier J, Hetzer C, Seelam RR, Phelan BT, Krzyaniak MD, Volland M, Brana Coto P, Young RM, Clark T, Thoss M, Tykwinski R, Wasielewski MR, Guldi DM
Journal: Chem
Publisher: CELL PRESS
Publication year: 2018
Volume: 4
Journal issue: 5
Pages range: 1092-1111
ISSN: 2451-9308
eISSN: 2451-9294


Abstract

Singlet fission (SF) is a process that converts one singlet excited state into two triplet states. The mechanism of SF is still not well understood. Here, we report on the use of a combination of transient absorption and electron paramagnetic resonance spectroscopies in conjunction with theoretical calculations to probe SF in a pentacene dimer linked by a non-conjugated, 1,4-diethynylbicyclo[2.2.2]octane spacer. Next to observing the key intermediates in solution-based SF, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons, we demonstrate that the coupling is sufficiently weak that SF is essentially inoperative in non-polar media. Transitioning to a polar medium, however, amplifies the coupling strength such that SF becomes operative and supports long triplet lifetimes. Our results offer strong evidence for a charge-transfer mediation and, in turn, provide a solid framework for decoding the complete mechanism of SF in systems beyond pentacene.


FAU Authors / FAU Editors

Basel, Bettina
Lehrstuhl für Physikalische Chemie I
Brana Coto, Pedro Dr.
Professur für Theoretische Physik mit dem Schwerpunkt Elektronentransport in Molekülen
Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum
Guldi, Dirk Michael Prof. Dr.
Lehrstuhl für Physikalische Chemie I
Hetzer, Constantin
Lehrstuhl für Anorganische und Allgemeine Chemie
Seelam, Rajagopala Reddy, Ph.D.
Professur für Theoretische Physik mit dem Schwerpunkt Elektronentransport in Molekülen
Thoss, Michael Prof. Dr.
Professur für Theoretische Physik mit dem Schwerpunkt Elektronentransport in Molekülen
Tykwinski, Rik Prof.
Lehrstuhl für Organische Chemie I
Volland, Michel
Lehrstuhl für Physikalische Chemie I
Zirzlmeier, Johannes
Lehrstuhl für Physikalische Chemie I


External institutions with authors

Northwestern University


How to cite

APA:
Basel, B., Zirzlmeier, J., Hetzer, C., Seelam, R.R., Phelan, B.T., Krzyaniak, M.D.,... Guldi, D.M. (2018). Evidence for Charge-Transfer Mediation in the Primary Events of Singlet Fission in a Weakly Coupled Pentacene Dimer. Chem, 4(5), 1092-1111. https://dx.doi.org/10.1016/j.chempr.2018.04.006

MLA:
Basel, Bettina, et al. "Evidence for Charge-Transfer Mediation in the Primary Events of Singlet Fission in a Weakly Coupled Pentacene Dimer." Chem 4.5 (2018): 1092-1111.

BibTeX: 

Last updated on 2019-13-01 at 07:09