Photoinduced electron transfer fluorescence switching

Keywords Luminescence m Fluorescence m Phosphorescence a Sensors a Switches a Logic Gates a Supramolecular Systems a Truth Tables a Photoinduced Electron Transfer a Molecular-Level Devices... 

TTF-based D-A systems have been extensively used in recent years to play around photoinduced electron transfer processes. Typically, when an electron acceptor moiety that emits fluorescence intrinsically is linked to TTF (D), the fluorescence due to the A moiety may be quenched because of a photoinduced electron transfer process (Scheme 15.1). Accordingly, these molecular systems are potentially interesting for photovoltaic studies. For instance, efficient photoinduced electron transfer and charge separation were reported for TTF-fullerene dyads.6,7 An important added value provided by TTF relies on the redox behavior of this unit that can be reversibly oxidized according to two successive redox steps. Therefore, such TTF-A assemblies allow an efficient entry to redox fluorescence switches, for which the fluorescent state of the fluorophore A can be reversibly switched on upon oxidation of the TTF unit. 

Ferrocene has been widely investigated as an electron donor and its electron donating ability can be tuned by redox reactions. As anticipated, when a ferrocene unit is covalently connected to an electron acceptor moiety that shows intrinsic fluorescence, the fluorescence of the acceptor moiety would be largely quenched because of the photoinduced electron transfer between ferrocene and the fluorescent acceptor. For instance, triad 15 that contains perylene diimide flanked by two ferrocene moieties, shows rather weak fluorescence due to the photoinduced electron transfer between perylene diimide and ferrocene units. Either chemical or electrochemical oxidation of ferrocene unit lead to fluorescence enhancement. This is simply because the electron donating ability of ferrocene is reduced after oxidation and accordingly the photoinduced electron transfer is prohibited. In this way, the fluorescence intensity of 15 can be reversibly modulated by sequential electrochemical oxidation and reduction. Therefore, a new redox fluorescence switch can be established with triad 15.25... 

Green plant photosynthesis, which feeds the world, runs on photoinduced electron transfer (PET). 121 This principle was developed in chemical contexts by Albert Weller over three decades ago, 131 and became adapted for use in fluorescent switching contexts in the late 1970s and early 1980s. 14-211 A general design principle emerged soon afterwards. 221... 

Switching systems based on photochromic behavior,I29 43,45 77-100 optical control of chirality,175 76 1011 fluorescence,[102-108] intersystem crossing,[109-113] electro-chemically and photochemical induced changes in liquid crystals,l114-119 thin films,170,120-1291 and membranes,[130,131] and photoinduced electron and energy transfer1132-1501 have been synthesized and studied. The fastest of these processes are intramolecular and intermolecular electron and energy transfer. This chapter details research in the development and applications of molecular switches based on these processes. 

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