Relationship between spatially heterogeneous reaction dynamics and photochemical kinetics in single crystals of anthracene derivatives,Chemical Science

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Relationship between spatially heterogeneous reaction dynamics and photochemical kinetics in single crystals of anthracene derivatives
Chemical Science ( IF 7.6 ) Pub Date : 2024-07-26 , DOI: 10.1039/d4sc03060e
Sogo Kataoka ₁ , Daichi Kitagawa ₁ , Hikaru Sotome ₂ , Syoji Ito ₂ , Hiroshi Miyasaka ₂ , Christopher J Bardeen ₃ , Seiya Kobatake ₁

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Understanding physicochemical property changes based on reaction kinetics is required to design materials exhibiting desired functions at arbitrary timings. In this work, we investigated the photodimerization of anthracene derivatives in single crystals. Single crystals of 9-cyanoanthracene (9CA) and 9-anthraldehyde (9AA) exhibited reaction front propagation on the optical length scale, while 9-methylanthracene and 9-acetylanthracene crystals underwent spatially homogeneous conversion. Moreover, the sigmoidal behavior in the absorbance change associated with the reaction was much pronounced in the case of 9CA and 9AA and correlated with the observation of heterogeneous reaction progress. A kinetic analysis based on the Finke–Watzky model showed that the effective quantum yield of the photochemical reaction changes by more than an order of magnitude during the course of the reaction in 9CA and 9AA. Both the reaction front propagation and nonlinear kinetic behavior could be rationalized in terms of the difference in the cooperativity of the reactions. We propose a plausible mechanism for the heterogeneous reaction progress in single crystals that depends on the magnitude of the conformational change required for reaction. Our results provide useful information to understand the connection between photochemical reaction progress in the crystalline phase and the dynamic changes in the physicochemical properties.

中文翻译：

蒽衍生物单晶空间非均相反应动力学与光化学动力学的关系

要设计在任意时间表现出所需功能的材料，需要了解基于反应动力学的物理化学性质变化。在这项工作中，我们研究了单晶中蒽衍生物的光二聚作用。 9-氰基蒽（ 9CA ）和9-蒽醛（ 9AA ）的单晶在光学长度尺度上表现出反应前沿传播，而9-甲基蒽和9-乙酰蒽晶体则经历空间均匀转换。此外，在9CA和9AA的情况下，与反应相关的吸光度变化的 S 形行为非常明显，并且与异质反应进展的观察相关。基于Finke-Watzky模型的动力学分析表明， 9CA和9AA的光化学反应的有效量子产率在反应过程中发生了超过一个数量级的变化。反应前沿传播和非线性动力学行为都可以根据反应协同性的差异来合理化。我们提出了一种单晶异相反应进程的合理机制，该机制取决于反应所需构象变化的幅度。我们的结果为理解晶相中的光化学反应进程与物理化学性质的动态变化之间的联系提供了有用的信息。

更新日期：2024-07-26

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