Singlet Exciton Fission in Polycrystalline Thin Films of a Slip-Stacked Perylenediimide

• Published in: Journal of the American Chemical Society Vol. 135; no. 39; pp. 14701 - 14712
• Main Authors: Eaton, Samuel W, Shoer, Leah E, Karlen, Steven D, Dyar, Scott M, Margulies, Eric A, Veldkamp, Brad S, Ramanan, Charusheela, Hartzler, Daniel A, Savikhin, Sergei, Marks, Tobin J, Wasielewski, Michael R
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 02.10.2013; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; crystal structure; photosynthesis; photovoltaic cells; Physical Sciences; Science & Technology; X-ray diffraction; TRIPLET EXCITONS; PHOTOINDUCED ELECTRON-TRANSFER; EXCIMER-FORMING CRYSTAL; RHODOSPIRILLUM-RUBRUM; TETRACENE CRYSTALS; SPIN-RESONANCE; CHARGE SEPARATION; ENERGY-TRANSFER; MAGNETIC-FIELD; PHOTOSYNTHETIC SYSTEM
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/ja4053174

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 τSF = 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.