Influence of Charge Distribution on Structural Changes of Aromatic Imide Derivatives upon One-Electron Reduction Revealed by Time-Resolved Resonance Raman Spectroscopy during Pulse Radiolysis
- Authors
- Zhuang, Bo; Fujitsuka, Mamoru; Tojo, Sachiko; Cho, Dae Won; Choi, Jungkweon; Majima, Tetsuro
- Issue Date
- 8-11월-2018
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF PHYSICAL CHEMISTRY A, v.122, no.44, pp.8738 - 8744
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF PHYSICAL CHEMISTRY A
- Volume
- 122
- Number
- 44
- Start Page
- 8738
- End Page
- 8744
- URI
- https://scholar.korea.ac.kr/handle/2021.sw.korea/71868
- DOI
- 10.1021/acs.jpca.8b08310
- ISSN
- 1089-5639
- Abstract
- Structural changes of aromatic imides upon one-electron reduction are investigated by time-resolved resonance Raman spectroscopy during pulse radiolysis. Significant downshifts are observed for both the aromatic ring stretching and carbonyl stretching modes, which are related to a reduction of the bond order and increase of the charge density on these moieties. For three aromatic imides, i.e., 1,8 -naphthalene imide (1,8-NI), 2,3-naphthalene imide (2,3-NI), and naphthalene diimide (NDI), the extent of structural changes is found to follow the order: 2,3-NI > 1,8-NI > NDI, reflecting the influence of charge distribution on molecular structure. To further investigate this phenomenon, a series of homologous NDI derivatives with a substituted phenyl group at the imide position are studied. The Raman peaks between 1550 and 1600 cm(-1) which are assigned to aromatic stretching vibrations of the NDI moieties, are found to be sensitive to the charge distribution: stronger electron-withdrawing substituents result in these peaks shifting to slightly higher wavenumbers. As supported by a spin density analysis, despite the fact that the added charge is mostly localized on the NDI moiety, in the presence of an electron-withdrawing group, the subtle charge is likely to delocalize on the phenyl fragment, alleviating the effect of one-electron reduction on the molecular structure.
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