title: Excimer formation in cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) dimers on a redox-inactive triptycene scaffold.
abstract: Excitation energy transfer in perylene-3,4:9,10-bis(dicarboximide) (PDI) aggregates is of interest for light-harvesting applications of this strongly absorbing and π-π stacking chromophore. Here we report the synthesis and characterization of two PDI dimers in which the chromophores are covalently linked by a redox-inactive triptycene bridge in orientations that are cofacial (1) and slip-stacked along their N-N axes (2). Femtosecond transient absorption experiments on 1 and 2 reveal rapid exciton delocalization resulting excimer formation. Cofacial π-π stacked dimer 1 forms a low-energy excimer state absorption (λmax = 1666 nm) in τ = ∼2 ps after photoexcitation. Inserting a phenyl spacer on the bridge to generate a slip-stacked PDI-PDI geometry in 2 results in a less stable excimer state (λmax = 1430 nm), which forms in τ = ∼12 ps due to decreased electronic coupling. The near-infrared (NIR) excimer absorption of cofacial dimer 1 is ∼120 meV lower in energy than that of slip-stacked dimer 2, further highlighting electronic differences between these states.
authors.affiliation: Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208-3113, USA. m-wasielewski@northwestern.edu.
authors.forename: Eric A
authors.initials: EA
authors.lastname: Margulies
authors.forename: Leah E
authors.initials: LE
authors.lastname: Shoer
authors.forename: Samuel W
authors.initials: SW
authors.lastname: Eaton
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski