Magne Chloe, Streckaite Simona, Boto Roberto A, Domínguez-Ojeda Eduardo, Gromova Marina, Echeverri Andrea, Brigiano Flavio Siro, Ha-Thi Minh-Huong, Fanckevičius Marius, Jašinskas Vidmantas, Quaranta Annamaria, Pascal Andrew A, Koepf Matthieu, Casanova David, Pino Thomas, Robert Bruno, Contreras-García Julia, Finkelstein-Shapiro Daniel, Gulbinas Vidmantas, Llansola-Portoles Manuel J
Université Paris-Saclay, CEA, CNRS, Institute for Integrative Biology of the Cell (I2BC) Gif-sur-Yvette 91190 France
Department of Molecular Compound Physics, Center for Physical Sciences and Technology Saulėtekio Avenue 3 Vilnius LT-10257 Lithuania.
Chem Sci. 2024 Oct 4;15(43):17831-42. doi: 10.1039/d4sc04732j.
We provide direct evidence of singlet fission occurring with water-soluble compounds. We show that perylene-3,4,9,10-tetracarboxylate forms dynamic dimers in aqueous solution, with lifetimes long enough to allow intermolecular processes such as singlet fission. As these are transient dimers rather than stable aggregates, they retain a significant degree of disorder. We performed a comprehensive analysis of such dynamic assemblies using time-resolved absorption and fluorescence spectroscopy, nuclear magnetic resonance spectroscopy, and theoretical modelling, allowing us to observe the characteristic signatures of singlet fission and develop a model to characterize the different species observed. Our findings reveal that structure fluctuations within perylene-3,4,9,10-tetracarboxylate associations are key in favoring either singlet fission or charge separation. The efficiency of triplet formation is higher than 100%, and the disordered system leads to triplets living in the nanosecond time range.
我们提供了水溶性化合物发生单重态裂变的直接证据。我们表明，苝-3,4,9,10-四羧酸酯在水溶液中形成动态二聚体，其寿命足够长，能够允许诸如单重态裂变等分子间过程发生。由于这些是瞬态二聚体而非稳定聚集体，它们保持着显著程度的无序性。我们使用时间分辨吸收和荧光光谱、核磁共振光谱以及理论建模对这类动态组装体进行了全面分析，这使我们能够观察到单重态裂变的特征信号，并开发出一个模型来表征所观察到的不同物种。我们的研究结果表明，苝-3,4,9,10-四羧酸酯缔合体内的结构波动对于促进单重态裂变或电荷分离至关重要。三重态形成的效率高于100%，并且无序系统导致三重态的寿命处于纳秒时间范围。
