Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide
The intramolecular charge transfer (ICT) of 1-aminoanthraquinone (AAQ) in the excited state strongly depends on its solvent properties, and the twisted geometry of its amino group has been recommended for the twisted ICT (TICT) state by recent theoretical works. We report the transient Raman spectra...
Guardado en:
Autores principales: | , , , , |
---|---|
Formato: | article |
Lenguaje: | EN |
Publicado: |
MDPI AG
2021
|
Materias: | |
Acceso en línea: | https://doaj.org/article/25fe52fd4e214b09b368cfab2bd510f6 |
Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
id |
oai:doaj.org-article:25fe52fd4e214b09b368cfab2bd510f6 |
---|---|
record_format |
dspace |
spelling |
oai:doaj.org-article:25fe52fd4e214b09b368cfab2bd510f62021-11-11T17:20:37ZIntramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide10.3390/ijms2221119261422-00671661-6596https://doaj.org/article/25fe52fd4e214b09b368cfab2bd510f62021-11-01T00:00:00Zhttps://www.mdpi.com/1422-0067/22/21/11926https://doaj.org/toc/1661-6596https://doaj.org/toc/1422-0067The intramolecular charge transfer (ICT) of 1-aminoanthraquinone (AAQ) in the excited state strongly depends on its solvent properties, and the twisted geometry of its amino group has been recommended for the twisted ICT (TICT) state by recent theoretical works. We report the transient Raman spectra of AAQ in a dimethylsulfoxide (DMSO) solution by femtosecond stimulated Raman spectroscopy to provide clear experimental evidence for the TICT state of AAQ. The ultrafast (~110 fs) TICT dynamics of AAQ were observed from the major vibrational modes of AAQ including the ν<sub>C-N</sub> + δ<sub>CH</sub> and ν<sub>C=O</sub> modes. The coherent oscillations in the vibrational bands of AAQ strongly coupled to the nuclear coordinate for the TICT process have been observed, which showed its anharmonic coupling to the low frequency out of the plane deformation modes. The vibrational mode of solvent DMSO, ν<sub>S=O</sub> showed a decrease in intensity, especially in the hydrogen-bonded species of DMSO, which clearly shows that the solvation dynamics of DMSO, including hydrogen bonding, are crucial to understanding the reaction dynamics of AAQ with the ultrafast structural changes accompanying the TICT.Kooknam JeonMyungsam JenSebok LeeTaehyung JangYoonsoo PangMDPI AGarticleintramolecular charge transferexcited-state dynamicssolvation dynamicscoherent oscillationsfemtosecond stimulated Raman spectroscopyBiology (General)QH301-705.5ChemistryQD1-999ENInternational Journal of Molecular Sciences, Vol 22, Iss 11926, p 11926 (2021) |
institution |
DOAJ |
collection |
DOAJ |
language |
EN |
topic |
intramolecular charge transfer excited-state dynamics solvation dynamics coherent oscillations femtosecond stimulated Raman spectroscopy Biology (General) QH301-705.5 Chemistry QD1-999 |
spellingShingle |
intramolecular charge transfer excited-state dynamics solvation dynamics coherent oscillations femtosecond stimulated Raman spectroscopy Biology (General) QH301-705.5 Chemistry QD1-999 Kooknam Jeon Myungsam Jen Sebok Lee Taehyung Jang Yoonsoo Pang Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
description |
The intramolecular charge transfer (ICT) of 1-aminoanthraquinone (AAQ) in the excited state strongly depends on its solvent properties, and the twisted geometry of its amino group has been recommended for the twisted ICT (TICT) state by recent theoretical works. We report the transient Raman spectra of AAQ in a dimethylsulfoxide (DMSO) solution by femtosecond stimulated Raman spectroscopy to provide clear experimental evidence for the TICT state of AAQ. The ultrafast (~110 fs) TICT dynamics of AAQ were observed from the major vibrational modes of AAQ including the ν<sub>C-N</sub> + δ<sub>CH</sub> and ν<sub>C=O</sub> modes. The coherent oscillations in the vibrational bands of AAQ strongly coupled to the nuclear coordinate for the TICT process have been observed, which showed its anharmonic coupling to the low frequency out of the plane deformation modes. The vibrational mode of solvent DMSO, ν<sub>S=O</sub> showed a decrease in intensity, especially in the hydrogen-bonded species of DMSO, which clearly shows that the solvation dynamics of DMSO, including hydrogen bonding, are crucial to understanding the reaction dynamics of AAQ with the ultrafast structural changes accompanying the TICT. |
format |
article |
author |
Kooknam Jeon Myungsam Jen Sebok Lee Taehyung Jang Yoonsoo Pang |
author_facet |
Kooknam Jeon Myungsam Jen Sebok Lee Taehyung Jang Yoonsoo Pang |
author_sort |
Kooknam Jeon |
title |
Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
title_short |
Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
title_full |
Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
title_fullStr |
Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
title_full_unstemmed |
Intramolecular Charge Transfer of 1-Aminoanthraquinone and Ultrafast Solvation Dynamics of Dimethylsulfoxide |
title_sort |
intramolecular charge transfer of 1-aminoanthraquinone and ultrafast solvation dynamics of dimethylsulfoxide |
publisher |
MDPI AG |
publishDate |
2021 |
url |
https://doaj.org/article/25fe52fd4e214b09b368cfab2bd510f6 |
work_keys_str_mv |
AT kooknamjeon intramolecularchargetransferof1aminoanthraquinoneandultrafastsolvationdynamicsofdimethylsulfoxide AT myungsamjen intramolecularchargetransferof1aminoanthraquinoneandultrafastsolvationdynamicsofdimethylsulfoxide AT seboklee intramolecularchargetransferof1aminoanthraquinoneandultrafastsolvationdynamicsofdimethylsulfoxide AT taehyungjang intramolecularchargetransferof1aminoanthraquinoneandultrafastsolvationdynamicsofdimethylsulfoxide AT yoonsoopang intramolecularchargetransferof1aminoanthraquinoneandultrafastsolvationdynamicsofdimethylsulfoxide |
_version_ |
1718432105939075072 |