Ultrafast Excited-State Intermolecular Proton Transfer in Indigo Oligomer

被引:16
|
作者
He, Xuemei [1 ,5 ]
Yang, Fan [1 ,2 ]
Li, Shuang [3 ]
He, Xiaoxiao [4 ]
Yu, Anchi [3 ]
Chen, Jinquan [4 ]
Xu, Jianhua [4 ]
Wang, Jianping [1 ,2 ]
机构
[1] Chinese Acad Sci, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China
[2] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[3] Renmin Univ China, Dept Chem, Beijing 100872, Peoples R China
[4] East China Normal Univ, State Key Lab Precis Spect, Shanghai 200062, Peoples R China
[5] Jiangxi Agr Univ, Dept Chem, Sch Sci, Nanchang 330045, Jiangxi, Peoples R China
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2019年 / 123卷 / 30期
基金
中国国家自然科学基金;
关键词
H STRETCHING MODES; DYNAMICS; SPECTROSCOPY; DERIVATIVES; PHOTOSTABILITY; SYSTEMS; PROBE;
D O I
10.1021/acs.jpca.9b06427
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
It has been a long-lasting debate whether indigo undergoes excited-state proton transfer and how this contributes to its photostability. A prevailing point of view is that a sub-picosecond excited-state intramolecular single proton transfer occurs; however, it has been studied mostly under dilute solution conditions. In this work, excited-state structural dynamics of indigo oligomers formed at millimolar concentration in dimethyl sulfoxide is investigated using femtosecond visible pump spectroscopy, infrared and visible probe spectroscopies, and steady-state infrared and fluorescence spectroscopies. Experimental evidence indicates the presence of transient intermolecular electronic excited-state proton transfer, which is supported by quantum-chemistry computations. The formed enol species disappears with a time constant of 200-300 fs, followed by a relatively slow nonradiative relaxation to the electronic ground state. Our results reveal new photochemistry of indigo particularly in its oligomeric state.
引用
收藏
页码:6463 / 6471
页数:9
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