Conjugation Length Dependence of Intramolecular Singlet Fission in a Series of Regioregular Oligo 3-Alkyl(thienylene-vinylene)s

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Daniel W. Polak, Iain Andrews, Enrico Salvadori, Andrew J. Musser, Alexander Auty, Dimitri Chekulaev, Julia A. Weinstein, Martin Heeney, Jenny Clark
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引用次数: 0

Abstract

Activated intramolecular singlet fission is known to occur in the conjugated polymer polythienylene-vinylene (P3TV). Instead, efficient intersystem crossing has been observed in a short 3-alkyl(thienylene-vinylene) dimer. Here, we investigate a series of oligomers covering the conjugation length gap between the dimer and polymer. We confirm that the polymer and longer oligomers undergo activated intramolecular singlet fission, while the shorter oligomers with less than 3 units predominantly undergo efficient intersystem crossing. For the longer oligomers, the intermediate state of singlet fission is assigned to the 3Ag covalent state of triplet pair character, as predicted by several computational studies. Our results point to potential pitfalls when assigning triplet production pathways solely with transient absorption spectroscopy.

Abstract Image

区域规则低聚3-烷基(乙烯-乙烯)分子内单线态裂变的共轭长度依赖性
已知活化的分子内单线态裂变发生在共轭聚合物聚乙烯-乙烯(P3TV)中。相反,在短的3-烷基(乙烯-乙烯)二聚体中观察到有效的体系间交叉。在这里,我们研究了一系列覆盖二聚体和聚合物之间的共轭长度间隙的低聚物。我们证实,聚合物和较长的低聚物发生激活的分子内单线态裂变,而少于3个单位的较短的低聚物主要发生有效的系统间交叉。对于较长的低聚体,单重态裂变的中间态被分配到三重态特征的3Ag共价态,正如一些计算研究所预测的那样。我们的研究结果指出了当用瞬态吸收光谱分配三重态生产途径时可能存在的缺陷。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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