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Advances in electrochemical science and engineering by Richard C. Alkire, Charles W. Tobias

By Richard C. Alkire, Charles W. Tobias

This sequence, previously edited by way of Heinz Gerischer and Charls V. Tobias, now edited via Richard C. Alkire and Dieter M. Kolb, has been warmly welcomed via scientists world-wide that's mirrored within the stories of the former volumes: 'This is a vital publication for researchers in electrochemistry; it covers components of either primary and functional significance, with experiences of top quality. the fabric is particularly good provided and the alternative of subject matters displays a balanced editorial coverage that's welcomed.' The Analyst

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On the other hand, the crystallographic data for 1-(pdiethylani1ino)naphthalene [ 1391 indicate that such a quinoid structure is already present, at least partially, in the compounds studied. The diethylamino group is almost co-planar with the phenylene ring with the C-N bond length only * 42 A. 143 nm [160]). This suggests that the structural changes in the donor subunit of A-D, accompanying oxidation to the radical cation, should be not very significant. 002nm) [161]. Similar changes are also expected for other arenes (or acridine) used as the acceptor subunits in the compounds studied.

The preference for the given reaction pathway is related to the free-energy difference between the oxidized and reduced precursors. The formation of the excited product requires this difference to be equal to or higher than the energy difference between the excited and ground electronic states. Therefore, only an energy-sufficient system may generate the fluorescent singlet state. The emitting singlet state may be formed directly upon electron transfer from R- to R+ (the S-route). The emissive singlet R* undergoes radiative deactivation (with quantum yield qho): ' 'R* -+ R hc& (36) Obviously, if the electron transfer reaction is energetically sufficient to populate the excited singlet directly, formation of lower-lying excited triplets must also take place (T-route).

2 Intramolecular Donor-Acceptor Systems The S-route for electrochemical generation of the excited states is expected to be favored for a system where the luminescence originates from the low-lying excited states. For organic compounds, it may be expected that some of the systems which exhibit a large Stokes shift should involve the direct formation of the emitting species. A large Stokes shift is observed for those molecules whch change their structure greatly after excitation. Intramolecular charge transfer in systems containing large n-aromatic donor (D) and acceptor (A) subunits may be an example.

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