By Richard C. Alkire, Charles W. Tobias
This sequence, previously edited via Heinz Gerischer and Charls V. Tobias, now edited by means of 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 necessary ebook for researchers in electrochemistry; it covers parts of either primary and functional value, with experiences of top of the range. the cloth is particularly good provided and the alternative of themes displays a balanced editorial coverage that's welcomed.' The Analyst
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Therefore one may expect that ECL system in which the lowest excited state 45 Marcus Theory in the Description of Electrochemiluminescence Phenomena N 2,2'-bipyridine 4,7-diphenyl- N "0 2,2'-bipyrazine 2,2'-biisoquinoline 2,2'-biquinoline bPZ biq bqu 1,lo-phenanthroline bPY dPh Fig. 24. Examples of the bidentate ligands forming electrochemiluminescent ruthenium(I1) complexes. is the emitter should be much more efficient. In fact, in some ECL systems involving transition-metal complexes (in which phosphorescence is allowed by the spin-orbit coupling) ECL yields approach the luminescence quantum yield, indicating that the emitting state is produced with an efficiency near unity.
The formation of the excited singlet is the least (if at all) exergonic and much less thermodynamically favored. 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).
As previously mentioned, the optical transition moment M of the given exciplex is related to the electronic coupling element V according to Cannon : where ,LLCT are the static dipole moment and the energy of the given exciplex. 01 eV. For the reactions producing the excited intramolecular charge-transfer states (reactions (62) and (63)), the electron transfer processes occur at the greater distance, r12 A r (see Fig. 21). Since the electronic coupling elements decrease exponentially with distance, VCT may be expressed as follows: + with p equal to 10-12nm-'.
Advances in electrochemical science and engineering by Richard C. Alkire, Charles W. Tobias