Rational Design of Triplet Sensitizers for the Transfer of Excited State Photochemistry from UV to Visible
Rational Design of Triplet Sensitizers for the Transfer of Excited State Photochemistry from UV to Visible
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DOI：
10.1021/jacs.0c05069
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发表时间：
2020-09-02
影响因子：
15
通讯作者：
Booker-Milburn, Kevin
中科院分区：
文献类型：
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作者：
Elliott, Luke D.;Kayal, Surajit;Booker-Milburn, Kevin
利用含时密度泛函理论设计合成了一系列噻吨酮三重态敏化剂。计算的三重激发态（E-T）的能量通知的类型和位置的助色剂放置在噻吨酮核心，使微调的紫外可见光谱和相关的三重态能量。计算结果在λ（max）和E-T值的量级上都与实验观测值高度一致。合成的化合物，然后评价其作为三重态敏化剂在各种UV和可见光制备光化学反应的效力。这项研究的结果超出了预期;特别是发现先前在UV中敏化的[2 + 2]环加成化学在455 nm（蓝色）处进行环加成，相对于输入功率，生产率（g/h）增加了2至9倍。这项研究表明，强大的现代计算方法的能力，以帮助设计成功的和富有成效的三重态敏化光化学反应。
Time Dependent Density Functional Theory has been used to assist the design and synthesis of a series thioxanthone triplet sensitizers. Calculated energies of the triplet excited state (E-T) informed both the type and position of auxochromes placed on the thioxanthone core, enabling fine-tuning of the UV-vis absorptions and associated triplet energies. The calculated results were highly consistent with experimental observation in both the order of the lambda(max) and E-T values. The synthesized compounds were then evaluated for their efficacies as triplet sensitizers in a variety of UV and visible light preparative photochemical reactions. The results of this study exceeded expectations; in particular [2 + 2] cycloaddition chemistry that had previously been sensitized in the UV was found to undergo cycloaddition at 455 nm (blue) with a 2- to 9-fold increase in productivity (g/h) relative to input power. This study demonstrates the ability of powerful modern computational methods to aid in the design of successful and productive triplet sensitized photochemical reactions.