期刊
SCIENCE CHINA-CHEMISTRY
卷 60, 期 5, 页码 607-613出版社
SCIENCE PRESS
DOI: 10.1007/s11426-016-0500-2
关键词
dicyanomethylene-4H-pyran; luminescence; redox switch; ferrocene
资金
- National Key Research and Development Program [2016YFA0200300]
- National Natural Science Foundation of China [21325625, 21636002]
- Natural Science Foundation of China [1607044]
- Fundamental Research Funds for the Central Universities [WJ1416005, 2016 MS108]
- Oriental Scholarship
- Science and Technology Commission of Shanghai Municipality [15XD1501400]
A novel versatile dicyanomethylene-4H-pyran (DCM) based derivative bearing ferrocenyl group (DCM-N-Fc) is designed as modulator to construct off-on logic operation. The optical properties of DCM-N-Fc are characterized by absorption and steady-state fluorescence technique, showing that the fluorescence from DCM chromophore via intramolecular charge transfer (ICT) is strongly quenched by photoinduced electron transfer (PET) process from ferrocene moiety. In contrast with the references (DCM-N and DCM-Fc), the fluorescence of DCM-N-Fc can be triggered by oxidizing ferrocenyl unit either chemically or electrochemically, exhibiting a characteristic emission modulation at around 610 nm with an electrofluorochromic behavior. Furthermore, the free energy and the fluorescence lifetime in the PET path verify the thermodynamic feasibility. Cyclic voltammetry, absorption spectroscopy, time-resolved fluorescence as well as DFT calculation have been used to elaborate the manipulation via both PET and ICT processes.
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