The Role of the Core Attachment Positioning in Triggering Intramolecular Singlet Exciton Fission in Perylene Diimide Tetramers

被引:13
作者
Muthike, Angelar K. [1 ]
Carlotti, Benedetta [2 ]
Madu, Ifeanyi K. [1 ]
Jiang, Hanjie [1 ]
Kim, Hyungjun [1 ,3 ]
Wu, Qinghe [4 ,5 ]
Yu, Luping [4 ,5 ]
Zimmerman, Paul M. [1 ]
Goodson, Theodore, III [1 ]
机构
[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA
[2] Univ Perugia, Dept Chem Biol & Biotechnol, I-06123 Perugia, Italy
[3] Incheon Natl Univ, Dept Chem, Incheon 22012, South Korea
[4] Univ Chicago, Dept Chem, Chicago, IL 60637 USA
[5] Univ Chicago, James Franck Inst, Chicago, IL 60637 USA
关键词
STACKED PERYLENE-3,4/9,10-BIS(DICARBOXIMIDE) DIMERS; EXCIMER FORMATION; CHARGE-TRANSFER; PHOTOPHYSICAL PROPERTIES; ELECTRON-ACCEPTORS; PENTACENE; STATE; TETRACENE; ABSORPTION; MECHANISM;
D O I
10.1021/acs.jpcb.1c02534
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Previous studies have proposed that the presence of a flexible pi-bridge linker is crucial in activating intramolecular singlet exciton fission (iSEF) in multichromophoric systems. In this study, we report the photophysical properties of three analogous perylene diimide (PDI) dendritic tetramers showing flexible/twisted pi-bridged structures with alpha- and beta-substitutions and a rigid/planar structure with a beta-fused ring (beta C) connection to a benzodithiophene-thiophene (BDT-Th) core. The rigidity and enhanced planarity of beta C lead to significant intramolecular charge transfer and triplet formation via an intersystem crossing pathway. Steady-state spectroscopic measurements reveal similar absorption and emission spectra for the alpha-tetramer and the parent PDI monomer. However, their fluorescence quantum yield is significantly different. The negligible fluorescence yield of the alpha-tetramer (0.04%) is associated with a competitive nonradiative decay pathway. Indeed, for this twisted compound in a high polar environment, a fast and efficient iSEF with a triplet quantum yield of 124% is observed. Our results show that the alpha-single-bond connections in the alpha compound are capable of interrupting the coupling among the PDI units, favoring iSEF. We propose that the formation of the double triplet ((1)[TT]) state is through a superposition of singlet states known as [S1S0]([TT])CT, which has been suggested previously for pentacene derivatives. Using steady-state and time-resolved spectroscopic experiments, we demonstrate that the conformational flexibility of the linker itself is necessary but not sufficient to allow iSEF. For the case of the other twisted tetramer, beta, the strong pi-pi co-facial interactions between the adjacent PDI units in its structure lead to excimer formation. These excimer states trap the singlet excitons preventing the formation of the (1)[TT] state, thus inhibiting iSEF.
引用
收藏
页码:5114 / 5131
页数:18
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