Electronic and Structural Properties of 2,3‐Naphthalimide in Open‐Shell Configurations Investigated by Pulse Radiolytic and Theoretical Approaches
Electronic and Structural Properties of 2,3‐Naphthalimide in Open‐Shell Configurations Investigated by Pulse Radiolytic and Theoretical Approaches
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DOI：
10.1002/slct.202100417
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发表时间：
2021-04
期刊：
影响因子：
2.1
通讯作者：
Bo Zhuang;S. Tojo;M. Fujitsuka
中科院分区：
文献类型：
--
作者：
Bo Zhuang;S. Tojo;M. Fujitsuka
自由基离子和三重态激发态的结构表征通常具有挑战性，因为它们的高反应性和相应的短寿命，但可以通过脉冲辐射分解和时间分辨光谱技术相结合来实现。本文报道了一种基本芳香亚胺化合物2,3 -萘酰亚胺的瞬态吸收和时间分辨共振拉曼光谱，在脉冲辐射分解过程中记录了自由基阴离子和最低三重态。观察到这些瞬态物种的明显光谱特征，在理论计算的背景下进一步探讨。我们发现2,3 -萘酰亚胺在开壳构型下的分子结构与在萘基和羰基区域的自旋密度以及由于电子构型的改变而导致的局部芳构性的降低密切相关。特别是，我们的结果表明，尽管在中性基态和最低三重态2,3 -萘酰亚胺作为对称分子存在，但在其自由基阴离子状态下，添加一个电子会导致具有不寻常的面内不对称性的变形结构。
Structural characterization of radical ions and triplet excited states is usually challenging because of their high reactivity and corresponding short lifetime, but can be achieved by combining pulse radiolysis and time‐resolved spectroscopic techniques. Herein, we report the transient absorption and time‐resolved resonance Raman spectra of the radical anionic and the lowest triplet states of a fundamental aromatic imide compound, 2,3‐naphthalimide, recorded during pulse radiolysis. Distinct spectral features are observed for these transient species, which are further explored in the context of theoretical calculations. We found that the molecular structures of 2,3‐naphthalimide in open‐shell configurations are closely related to the spin density localised on the naphthyl and carbonyl regions, as well as the decrease in local aromaticity because of changes of electron configurations. In particular, our results demonstrate that although in the neutral ground state and the lowest triplet state 2,3‐naphthalimide exists as a symmetric molecule, in its radical anionic state, the addition of an electron leads to a deformed structure with unusual in‐plane asymmetry.