Volume 9, Issue 1
Modulating N-H-Based Excited-State Intramolecular Proton Transfer by Different Electron-Donating/Withdrawing Substituents in 2-(2’-Aminophenyl)Benzothiazole Compounds

Dapeng Yang, Guang Yang, Min Jia, Xiaoyan Song, Qiaoli Zhang & Tianjie Zhang

J. At. Mol. Sci., 9 (2018), pp. 17-20.

Published online: 2018-10

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  • Abstract

At the B3LYP/6-311+G(d, p)/IEFPCM (in dichloromethane) theory level, the N-H-based excited-state intramolecular proton transfer (N-H-based ESIPT) process of 2-(2’-aminophenyl)benzothiazole (PBT-NH2) and its three derivatives 2-(2’-methylaminophenyl) benzothiazole(PBT-NHMe), 2-(2’-acetylaminophenyl)benzothiazole (PBT-NHAc) and 2-(2’-tosylaminophenyl) benzothiazole (PBT-NHTs) have been explored by the time-dependent density functional theory (TD-DFT) method. Our calculated hydrogen bond lengths and angles sufficiently confirm that the intramolecular hydrogen bonds $N_1-H$•••$N_2$ formed at the $S_0$ states of the four compounds should be significantly strengthened in the $S_1$ state, which are further supported by the results obtained based on the analyses of infrared spectra shifts. The scanned potential energy curves reveal that the energy barriers of the first singlet excited state of the four titled compounds along the ESIPT reactions are predicted at 8.74, 8.98, 6.72 and 1.69 kcal/mol, respectively, suggesting that the inclusion of a strong electron-withdrawing tosyl (Ts) group can remarkably facilitate the occurrence of the ESIPT reaction, while the involvement of an electron-donating methyl group has slight opposite effect on the ESIPT process of the amino-type hydrogen-bonding system.

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@Article{JAMS-9-17, author = {Dapeng Yang, Guang Yang, Min Jia, Xiaoyan Song, Qiaoli Zhang and Tianjie Zhang}, title = {Modulating N-H-Based Excited-State Intramolecular Proton Transfer by Different Electron-Donating/Withdrawing Substituents in 2-(2’-Aminophenyl)Benzothiazole Compounds}, journal = {Journal of Atomic and Molecular Sciences}, year = {2018}, volume = {9}, number = {1}, pages = {17--20}, abstract = {

At the B3LYP/6-311+G(d, p)/IEFPCM (in dichloromethane) theory level, the N-H-based excited-state intramolecular proton transfer (N-H-based ESIPT) process of 2-(2’-aminophenyl)benzothiazole (PBT-NH2) and its three derivatives 2-(2’-methylaminophenyl) benzothiazole(PBT-NHMe), 2-(2’-acetylaminophenyl)benzothiazole (PBT-NHAc) and 2-(2’-tosylaminophenyl) benzothiazole (PBT-NHTs) have been explored by the time-dependent density functional theory (TD-DFT) method. Our calculated hydrogen bond lengths and angles sufficiently confirm that the intramolecular hydrogen bonds $N_1-H$•••$N_2$ formed at the $S_0$ states of the four compounds should be significantly strengthened in the $S_1$ state, which are further supported by the results obtained based on the analyses of infrared spectra shifts. The scanned potential energy curves reveal that the energy barriers of the first singlet excited state of the four titled compounds along the ESIPT reactions are predicted at 8.74, 8.98, 6.72 and 1.69 kcal/mol, respectively, suggesting that the inclusion of a strong electron-withdrawing tosyl (Ts) group can remarkably facilitate the occurrence of the ESIPT reaction, while the involvement of an electron-donating methyl group has slight opposite effect on the ESIPT process of the amino-type hydrogen-bonding system.

}, issn = {2079-7346}, doi = {https://doi.org/10.4208/jams.030618.051518a}, url = {http://global-sci.org/intro/article_detail/jams/12742.html} }
TY - JOUR T1 - Modulating N-H-Based Excited-State Intramolecular Proton Transfer by Different Electron-Donating/Withdrawing Substituents in 2-(2’-Aminophenyl)Benzothiazole Compounds AU - Dapeng Yang, Guang Yang, Min Jia, Xiaoyan Song, Qiaoli Zhang & Tianjie Zhang JO - Journal of Atomic and Molecular Sciences VL - 1 SP - 17 EP - 20 PY - 2018 DA - 2018/10 SN - 9 DO - http://doi.org/10.4208/jams.030618.051518a UR - https://global-sci.org/intro/article_detail/jams/12742.html KW - N-H-based excited-state intramolecular proton transfer, electron-donating/withdrawing substituents, potential energy curves, TDDFT method. AB -

At the B3LYP/6-311+G(d, p)/IEFPCM (in dichloromethane) theory level, the N-H-based excited-state intramolecular proton transfer (N-H-based ESIPT) process of 2-(2’-aminophenyl)benzothiazole (PBT-NH2) and its three derivatives 2-(2’-methylaminophenyl) benzothiazole(PBT-NHMe), 2-(2’-acetylaminophenyl)benzothiazole (PBT-NHAc) and 2-(2’-tosylaminophenyl) benzothiazole (PBT-NHTs) have been explored by the time-dependent density functional theory (TD-DFT) method. Our calculated hydrogen bond lengths and angles sufficiently confirm that the intramolecular hydrogen bonds $N_1-H$•••$N_2$ formed at the $S_0$ states of the four compounds should be significantly strengthened in the $S_1$ state, which are further supported by the results obtained based on the analyses of infrared spectra shifts. The scanned potential energy curves reveal that the energy barriers of the first singlet excited state of the four titled compounds along the ESIPT reactions are predicted at 8.74, 8.98, 6.72 and 1.69 kcal/mol, respectively, suggesting that the inclusion of a strong electron-withdrawing tosyl (Ts) group can remarkably facilitate the occurrence of the ESIPT reaction, while the involvement of an electron-donating methyl group has slight opposite effect on the ESIPT process of the amino-type hydrogen-bonding system.

Dapeng Yang, Guang Yang, Min Jia, Xiaoyan Song, Qiaoli Zhang and Tianjie Zhang. (2018). Modulating N-H-Based Excited-State Intramolecular Proton Transfer by Different Electron-Donating/Withdrawing Substituents in 2-(2’-Aminophenyl)Benzothiazole Compounds. Journal of Atomic and Molecular Sciences. 9 (1). 17-20. doi:10.4208/jams.030618.051518a
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