title: Singlet exciton fission in polycrystalline thin films of a slip-stacked perylenediimide.
abstract: The crystal structure of N,N-bis(n-octyl)-2,5,8,11-tetraphenylperylene-3,4:9,10-bis(dicarboximide), 1, obtained by X-ray diffraction reveals that 1 has a nearly planar perylene core and π-π stacks at a 3.5 Å interplanar distance in well-separated slip-stacked columns. Theory predicts that slip-stacked, π-π-stacked structures should enhance interchromophore electronic coupling and thus favor singlet exciton fission. Photoexcitation of vapor-deposited polycrystalline 188 nm thick films of 1 results in a 140 ± 20% yield of triplet excitons ((3*)1) in τ(SF) = 180 ± 10 ps. These results illustrate a design strategy for producing perylenediimide and related rylene derivatives that have the optimized interchromophore electronic interactions which promote high-yield singlet exciton fission for potentially enhancing organic solar cell performance and charge separation in systems for artificial photosynthesis.
authors.affiliation: Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Samuel W
authors.initials: SW
authors.lastname: Eaton
authors.forename: Leah E
authors.initials: LE
authors.lastname: Shoer
authors.forename: Steven D
authors.initials: SD
authors.lastname: Karlen
authors.forename: Scott M
authors.initials: SM
authors.lastname: Dyar
authors.forename: Eric A
authors.initials: EA
authors.lastname: Margulies
authors.forename: Brad S
authors.initials: BS
authors.lastname: Veldkamp
authors.forename: Charusheela
authors.initials: C
authors.lastname: Ramanan
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Hartzler
authors.forename: Sergei
authors.initials: S
authors.lastname: Savikhin
authors.forename: Tobin J
authors.initials: TJ
authors.lastname: Marks
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski