Forster-type triplet energy transfer

As mentioned earlier, triplet energy transfer can occur by way of Forster-type through-space interactions [100] or via Dexter-type electron exchange [101], In the former case, the rate constant for Forster-type triplet energy transfer (kp) can be expressed as follows ... 

The distance between the chromophores Is approximately 21 8 as measured on molecular models and no ground state Interaction could be observed. In dioxane, the singlet energy transfer occurs by a Forster-type mechanism. On the basis of this mechanism, the distance can be calculated from the transfer efficiency. For [16a] a value of 21.211.6 X was found, while for [I6b] one obtained a value of 16.7 1.4 X. This latter discrepancy was explained on the basis of preferential orientation of the chromophores. That this phenomenon Indeed plays an Important role, was proved by Leermakers (59,60) In a series of indole alkaloids. The same author (59) also Illustrated the absence of triplet-triplet transfer at low temperature in compound [16b]. 

Fig. 11.6 Scheme illustrating various transfer processes from the host to the guest electron (hole) transfer from the host LUMO (HOMO) to the guest LUMO (HOMO), Forster-type energy transfer between singlet states and Dexter-type energy transfer from the host to the guest triplet state. The nature of the excitonic state is simplified for better clarity. 

Further evidence of Forster-type energy-transfer effects has been obtained for several excited triplet-state donors and several ground-state doublet nitroxyl radicals. Critical transfer distances of the order of 12—20 A were measured and were on good agreement with calculated values. 

For such a through-space energy transfer process, a Dexter-type mechanism[29] seems more likely than a Forster-type mechanism[30] because of the triplet character of the excited states involved and the close approach of the two partners. 

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