Design, Synthesis, and Dynamics of a Green Fluorescent Protein Fluorophore Mimic with an Ultrafast Switching Function
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- 作者：Marco Paolino ; Moussa Gueye ; Elisa Pieri ; Madushanka Manathunga ; Stefania Fusi ; Andrea Cappelli ; Loredana Latterini ; Danilo Pannacci ; Michael Filatov ; Jérémie Léonard ; Massimo Olivucci
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：August 10, 2016
- 年：2016
- 卷：138
- 期：31
- 页码：9807-9825
- 全文大小：1150K
- 年卷期：0
- ISSN：1520-5126
文摘
While rotary molecular switches based on neutral and cationic organic π-systems have been reported, structurally homologous anionic switches providing complementary properties have not been prepared so far. Here we report the design and preparation of a molecular switch mimicking the anionic p-HBDI chromophore of the green fluorescent protein. The investigation of the mechanism and dynamics of the E/Z switching function is carried out both computationally and experimentally. The data consistently support axial rotary motion occurring on a sub-picosecond time scale. Transient spectroscopy and trajectory simulations show that the nonadiabatic decay process occurs in the vicinity of a conical intersection (CInt) between a charge transfer state and a covalent/diradical state. Comparison of our anionic p-HBDI-like switch with the previously reported cationic N-alkyl indanylidene pyrrolinium switch mimicking visual pigments reveals that these similar systems translocate, upon vertical excitation, a similar net charge in the same axial direction.