Solvation Controlled Excited-State Planarization in a Push-Pull Pyrene Dye

被引：17

作者：

Guo, Yuanyuan ^{[2
,4
]}

Abeywickrama, Chathura S. ^{[1
]}

Huo, Dayujia ^{[3
]}

Kong, Jie ^{[2
,4
]}

Tao, Min ^{[2
,4
]}

Xia, Andong ^{[2
,4
]}

Pang, Yi ^{[1
]}

Wan, Yan ^{[2
,3
]}

机构：

[1] Univ Akron, Dept Chem, Akron, OH 44325 USA

[2] Chinese Acad Sci, Inst Chem, BNLMS, Key Lab Photochem, Beijing 100190, Peoples R China

[3] Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China

[4] Univ Chinese Acad Sci, Beijing 100049, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY C | 2020年 / 124卷 / 16期

关键词：

INTRAMOLECULAR CHARGE-TRANSFER; ELECTRON-TRANSFER; SOLVENT POLARITY; THIOFLAVIN-T; DYNAMICS; FLUORESCENCE; RELAXATION; VISCOSITY; FEMTOSECOND; LIFETIME;

D O I：

10.1021/acs.jpcc.0c00417

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：

The excited-state deactivation pathway of the push-pull pyrene derivative (EPP), a molecule emitting bright red fluorescence, has been studied in several solvents using quantum chemical calculations, femtosecond time-resolved fluorescence up-conversion spectroscopy, and femtosecond transient absorption spectra (fs-TA). From the steady-state spectra, EPP has shown a strong negatively solvatochromic behavior of the absorption spectra and non-solvatochromic emission spectra, revealing the decreased dipole moment upon excitation. Femtosecond upconversion measurements have shown interesting rise-decay kinetics at the red emission side and fs-TA spectra also feature the SE (stimulated emission) formed and new ESA (excited-state absorption) developed in all investigated solvents. The careful analysis of the data gathered from fluorescence up-conversion and fs-TA spectra, supported by DFT quantum chemical calculations and temperature-dependent fluorescence measurements, unambiguously pointed out the excited-state relaxation pathway of EPP is controlled by solvent stabilized planar intramolecular charge transfer (PICT) dynamics. This finding confirms the surrounding solvents as a significant factor that affects the rate of excited-state conformation changes.

引用

页码：8550 / 8560

页数：11

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