Electrically generated intramolecular

The fact that emission occurs from a K state, which is generated electrically rather than photochemically, is quite significant these are the first materials reported to exhibit electrically generated intramolecular proton transfer EGffT. The mechanism of formation of K by photoexcitation is well documented to occur by a rapid proton transfer from E (2P). However, the mechanism of formation of K by the new EGIPT reaction is yet to be elucidated. The simplest representation of the overall EGIPT reaction is given in eq. 1. 

E. Galoppini, M. A. Fox, Effect of the Electric Field Generated by the Helix Dipole on Photoinduced Intramolecular Electron Transfer in Dichromophoric Alpha-Hdical Peptides , J. Am. Chem. Soc 1996, 118, 2299-2300. 

Additional information about this Fc GO preparation has been reported elsewhere (112). The intramolecular electron transfer rate constant kmirn calculated using Eq. (36) equals 40 s-1 and is by a factor of 50 higher than that for the randomly modified GO (104). The distance separating the ferrocene unit and FAD in Fc GO is believed to be ca. 19 A, by 2 A shorter than in the most effective electrically contacted enzyme generated by the random modification of GO by ferrocene units. This information supports the hypothesis about the key locations of ferrocene groups that play the dominant role in the electrocatalysis (104). 

The spin relaxation of most quadrupolar nuclei is completely given by the interaction of the nuclear quadrupole moment, eQ, with the electric-field gradient (e.f.g.) at the nucleus. To a good approximation the e.f.g. is generated in most molecular liquids exclusively by intramolecular charges. The interaction fluctuates in time because of the reorientation of the X—D or... 

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