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题名: Experimental and theoretical study of the rotational reorientation dynamics of 7-animocoumarin derivatives in polar solvents: hydrogen-bonding effects
作者: Zhou, Panwang1;  Song, Peng1;  Liu, Jianyong1;  Han, Keli1;  He, Guozhong1
刊名: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
发表日期: 2009
DOI: 10.1039/b910043a
卷: 11, 期:41, 页:9440-9449
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: The rotational reorientation dynamics of 7-aminocoumarin derivatives with different alkylation degrees in methanol, dimethylformamide, and dimethyl sulfoxide have been investigated using femtosecond time-resolved stimulated emission pumping fluorescence depletion (FS TR SEP FD) spectroscopy. In addition to a long anisotropy decay time that accounts for the overall rotational relaxation of solutes, a short anisotropy decay time on the order of picoseconds or sub-picoseconds was also observed in hydrogen-bonding systems. Three types of hydrogen bonds involving the nitrogen lone pair, carbonyl group, and amino group of 7-aminocoumarin derivatives were denoted as types A, B, and C, respectively. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were carried out to investigate the geometric structures of isolated coumarins and hydrogen-bonded complexes in the ground and excited states, respectively. According to our results and analysis, the rapid anisotropy decays observed here in hydrogen-bonding systems may be associated with the strengthening of hydrogen bonds B or C, or both in the excited state of hydrogen-bonded coumarin-solvent complexes, and are independent of the breaking of hydrogen bond A. The strengthening of hydrogen bond C in the excited state of 7-aminocoumarin-DMF and 7-aminocoumarin-DMSO complexes has been demonstrated theoretically for the first time. Further experimental studies would be crucial to confirm this observation.
关键词[WOS]: INTERMOLECULAR ELECTRON-TRANSFER ;  COUMARIN LASER-DYES ;  DENSITY-FUNCTIONAL THEORY ;  EXCITED-STATE PROPERTIES ;  DIELECTRIC FRICTION ;  PHOTOPHYSICAL PROPERTIES ;  ULTRAFAST DYNAMICS ;  MOLECULAR ROTATION ;  NONDIPOLAR PROBES ;  UNUSUAL BEHAVIOR
语种: 英语
WOS记录号: WOS:000270795500016
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/141455
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China

Recommended Citation:
Zhou, Panwang,Song, Peng,Liu, Jianyong,et al. Experimental and theoretical study of the rotational reorientation dynamics of 7-animocoumarin derivatives in polar solvents: hydrogen-bonding effects[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2009,11(41):9440-9449.
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