Download file (4.26MB)
Download as zip (3.74MB)

コレクション

引用

説明:

A soluble heptacene derivative, 5,9,14,18-tetrakis(triisopropylsilylethynyl)-heptacene (TIPS-Hep), was synthesized in situ from an α-diketone precursor via the Strating–Zwanenburg reaction, and its photophysical properties were comprehensively characterized in both solution and thin-film states. In deoxygenated dilute tetrahydrofuran (THF) solution, TIPS-Hep exhibited monomeric behavior. Absorption peaks were observed at 671, 737, 820, and 970 nm, accompanied by a shoulder at 870 nm, while fluorescence peaks were observed at 894 and 961 nm with a fluorescence lifetime (τs) of <100 ps. Nanosecond transient absorption spectroscopy revealed a triplet lifetime (τT) of 19 μs and a triplet quantum yield (ΦISC) of ∼2%. The short excited-state lifetime in dilute solution was estimated to be 87 ps by femtosecond transient absorption spectroscopy and precludes efficient molecular encounters, indicating that singlet fission is unlikely and that intersystem crossing serves as the dominant pathway for triplet formation. This interpretation is supported by transient decay analysis, which revealed no kinetic signatures associated with SF. In contrast, solution-processed thin films of TIPS-Hep, generated in situ by photoirradiation of a spin-coated α-diketone precursor, exhibited faster and enhanced formation of the triplet excited states. Since multiple excited species are involved, several kinetic models were examined, and a sequential model based on a SF pathway (S1 + S0 → TT → 2T1) was identified as the most consistent with the experimental results. Global analysis of femtosecond transient absorption data with the sequential SF model assuming three species revealed high yields of correlated triplet pairs (TT, 75% at the maximum value of 100%) and independent triplets (T1, 20% at the maximum value of 200%). These results provide valuable mechanistic insights into the excited-state dynamics of higher acenes.

権利情報:

• Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International
  

キーワード: Singlet fission, higher acene, excited-state dynamics, photoreaction

刊行年月日: 2026-02-18

出版者: American Chemical Society (ACS)

掲載誌:

• Journal of the American Chemical Society (ISSN: 00027863) vol. 148 issue. 6 p. 6000-6011

研究助成金:

• Japan Society for the Promotion of Science JP20H05833, JP23H04876, JP24H01714, JP24H01713
• Japan Society for the Promotion of Science JP25K01751, JP24K01473, JP22K14556, JP24K01576,
• Japan Society for the Promotion of Science JPJSBP120243209
• Nagase Science Technology Foundation
• Tokyo Ohka Foundation for The Promotion of Science and Technology

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1021/jacs.5c14689

関連資料:

その他の識別子:

連絡先:

更新時刻: 2026-04-13 08:56:08 +0900

MDRでの公開時刻: 2026-04-13 10:23:12 +0900