Thermodynamic Control of Intramolecular Singlet Fission and Exciton Transport in Linear Tetracene Oligomers
Thermodynamic Control of Intramolecular Singlet Fission and Exciton Transport in Linear Tetracene Oligomers
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线性并四苯低聚物分子内单线态裂变和激子输运的热力学控制
DOI：
10.1002/anie.202217704
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Hasobe Taku
中科院分区：
文献类型：
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作者：
Nakamura Shunta;Sakai Hayato;Fuki Masaaki;Ooie Rikuto;Ishiwari Fumitaka;Saeki Akinori;Tkachenko Nikolai V.;Kobori Yasuhiro;Hasobe Taku
我们新合成了一系列均和杂并四苯（Tc）低聚物，提出了一种通过促进相关三重态对（TT）解离和通过分子内单重态裂变控制单个双三重态激子（T+T）的顺序激子捕获过程来实现线性低聚物中有效激子输运的分子设计策略。首先，通过比较Tc-homo-oligomers [（Tc）n：n=2，4，6]来检查熵增益对Tc单元数量的影响。然后，（Tc）→ Tc-杂-低聚物[TcF 3-（Tc）4-TcF 3]的比较揭示了熵增益的电子振动耦合效应。观察到的熵T+T形成的影响表明，激子迁移是合理的可能的TT状态的数量增加，通过增加Tc单位的数量和在终端TCF 3单位的电子振动水平。最后，我们成功地观察到高产率激子捕获过程（捕获三重态产率：ΦTrT= 176%）。
We newly synthesized a series of homo‐ and hetero‐tetracene (Tc) oligomers to propose a molecular design strategy for the efficient exciton transport in linear oligomers by promoting correlated triplet pair (TT) dissociation and controlling sequential exciton trapping process of individual doubled triplet excitons (T+T) by intramolecular singlet fission. First, entropic gain effects on the number of Tc units are examined by comparing Tc‐homo‐oligomers [(Tc)n:n=2, 4, 6]. Then, a comparison of (Tc)nand Tc‐hetero‐oligomer [TcF3‐(Tc)4‐TcF3] reveals the vibronic coupling effect for entropic gain. Observed entropic effects on the T+T formation indicated that the exciton migration is rationalized by number of possible TT states increased both by increasing the number of Tc units and by the vibronic levels at the terminal TcF3units. Finally, we successfully observed high‐yield exciton trapping process (trapped triplet yield:ΦTrT=176 %).