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Direct Observation of a Charge-Transfer State Preceding High-Yield Singlet Fission in Terrylenediimide Thin Films

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posted on 15.12.2016, 00:00 by Eric A. Margulies, Jenna L. Logsdon, Claire E. Miller, Lin Ma, Ethan Simonoff, Ryan M. Young, George C. Schatz, Michael R. Wasielewski
Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S1) into two triplet excitons (T1), provided that the overall process is exoergic, i.e., E(S1) > 2E(T1). We report on SF in thin polycrystalline films of two terrylene-3,4:11,12-bis­(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T1 yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their π systems. In contrast, when the TDI molecules are slip-stacked along their N–N axes in films of 2, fsTA shows excimer formation, followed by a 50% T1 yield.